Device Physics of Narrow Gap Semiconductors (Microdevices)

Microdevices: Physics and Fabrication Technologies

Series Editors Arden Sher SRI International Menlo Park, CA USA Marcy A. Berding Applied Optics Laboratory SRI International Menlo Park, CA USA

For other titles published in this series, go to http://www.springer.com/series/6269

Junhao Chu

•

Arden Sher

Device Physics of Narrow Gap Semiconductors

123

Junhao Chu National Laboratory for Infrared Physics Shanghai Institute of Technical Physics, CAS Shanghai 200083, China [email protected] and Laboratory of Polar Materials and Devices East China Normal University Shanghai 200241 [email protected]

Arden Sher SRI International (Retired) 333 Ravenswood Ave. Menlo Park CA 94025-3493, USA [email protected]

ISBN 978-1-4419-1039-4 e-ISBN 978-1-4419-1040-0 DOI 10.1007/978-1-4419-1040-0 Springer New York Dordrecht Heidelberg London Library of Congress Control Number: 2009932685 c Springer Science+Business Media, LLC 2010  All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media, LLC, 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks, and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)

Foreword

The subject of semiconductor science and technology gained importance in the latter half of the twentieth century with the first stages studies of research on group IV elements and III–V group binary compound semiconductors. Much of the early device work concentrated on PbSnTe alloys, but this material had several problems related to its high-dielectric constant. The III–V compound semiconductor with the narrowest gap was InSb (energy gap is 0.18 eV at room temperature) and was not suited to the mid-wave or long-wave infrared ranges. To satisfy the demand of the infrared detection technology, a narrow gap semiconductor alloy appeared in 1959, the ternary alloy Hg1x Cdx Te based on HgTe and CdTe, from which narrower bandgaps can be reached. By changing the composition value of x, it was possible to meet the demands of infrared detectors in several important wave bands. Meanwhile, some interesting physical properties appeared due to the narrower energy bandgap. It immediately attracted intensive research attention. Professional discussions related to this material appeared around 1976. In 1976, an international conference named “Narrow Gap Semiconductors” was initiated. From then on, several other conferences related to “II–VI Group Semiconductors” or “Narrow Gap Semiconductors” have been held, for example, the conferences sponsored by NATO. The scale of every conference was large so that their proceedings formed the basis of an important branch of semiconductor science. During this rapid developmental process, several proceedings and review papers related to this type of semiconductor were published. To my knowledge, this book is the first international treatise which fully reviews the research results of narrow gap semiconductors. One of the authors of this book, Professor Junhao Chu, has made many contributions to the field of narrow gap semiconductors. He is considered one of the most suitable authors for a comprehensive book on narrow gap semiconductor physics. He was invited to update the database of Hg-based semiconductors for the new versions of “Landolt-Bornstein: Numerical Data and Functional Relationships in Science and Technology” published in 1999 and 2008. It has been my pleasure to read this book and the authors’ previous book (“Physics and Properties of Narrow Gap Semiconductors,” Springer 2008) in detail. They explore many research fields of HgCdTe, including basic crystallographic properties and growth methods from early studies to present research, principles and measurements of physical phenomena, and so on. Therefore, this book is not only a

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necessary reference for those who undertake research, teaching, and industrial work on narrow gap materials, but also of value for those undertaking work related to all semiconductors. Prof. Ding-Yuan Tang Member of Chinese Academy of Sciences Shanghai Institute of Technical Physics, CAS

Preface

The physics of narrow gap semiconductors is an important branch of semiconductor science. Research into this branch focuses on a specific class of semiconductor materials which have narrow forbidden band gaps. Past studies on this specific class of semiconductor materials have revealed not only general physical principles applicable to all semiconductors, but also those unique characteristics originating from the narrow band gaps, and therefore have significantly contributed to science and technology. Historically, developments of narrow gap semiconductor physics have been closely related to the development of the science and technology of infrared optical electronics in which narrow gap semiconductors have played a vital role in detectors and emitters, and other high speed devices. This book is dedicated to the study of narrow gap semiconductors and their applications. It is expected that the present volume will be valuable not only in the understanding of the fundamental science of these materials but also the technology of infrared optical electronics. There have been several books published in this field in recent decades. In 1977, a British scientist, D. R. Lovett, published “Semimetals and Narrow-Band Gap Semiconductors” (Pion Limited, London). Later, German scientists R. Dornhaus and G. Nimtz published a comprehensive review article in 1978, whose second edition, “The Properties and Applications of the HgCdTe Alloy System, in Narrow Gap Semiconductors,” was reprinted by Springer in 1983 (Springer Tracts in Modern Physics, Vol. 98, p.119). These two documents included systematic discussions of the physical properties of narrow-gap semiconductors and are still important references in the field. In 1980, the 18th volume of the series “Semiconductors and Semimetals” (edited by R.K.Willardson and Albert C. Beer) in which very useful reviews were collected, was dedicated to HgCdTe semiconductor alloys and devices. In 1991, a Chinese scientist, Prof. D. Y. Tang, published an important article, “Infrared Detectors of Narrow Gap Semiconductors,” in the book “Research and Progress of Semiconductor Devices” (edited by S. W. Wang, Science Publishers, Beijing, p.1–107), in which the fundamental principles driving HgCdTe-based infrared radiation detector technology were comprehensively discussed. In addition, a handbook, “Properties of Narrow Gap Cadmium-based Compounds” (edited by P. Capper), was published in the United Kingdom in 1994. This handbook

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contains a number of research articles about the physical and chemical properties of HgCdTe narrow-gap semiconductors and presents various data and references about Cd-based semiconductors. This book, “Device Physics of Narrow Gap Semiconductors,” is the second in a two–volume sequence on narrow gap semiconductors. The first volume, “Physics and Properties of Narrow Gap Semiconductors,” (Springer 2008), focuses mainly on materials physics and fundamental properties. Both volumes describe a variety of narrow gap semiconductor materials and revealing the intrinsic physical principles that govern their behavior. In this book, narrow gap semiconductors are presented within the larger framework of semiconductor physics. In particular, a unique property of this book is its extensive collection of results of research deduced by Chinese scientists, including one of the authors of this book, although the results are integrated into the larger body of knowledge on narrow gap semiconductor materials and devices. In organizing the book, special attention was paid to bridging the gap between basic physical principles and frontier research. This is achieved through extensive discussions of various aspects of the frontier theoretical and experimental scientific issues and by connecting them to device-related technology. It is expected that both students and researchers working in relevant fields will benefit from this book. The effort was encouraged by Prof. D. Y. Tang. J. Chu is most grateful to Prof. D. Y. Tang’s critical reading of the manuscript and invaluable suggestions and comments. A. Sher is indebted to Prof. A-B Chen for invaluable suggestions. The authors are also grateful to numerous students and colleagues who over the years have offered valuable support during the writing of this book. They are Drs: Y. Chang, K. Liu, Y. S. Gui, X. C. Zhang, J. Shao, L. Chu, Y. Cai, B. Li, Z. M. Huang, X. L¨u, L. He, M. A. Berding, and S. Krishnamurthy. We are indebted to Professor M. W. M¨uller for his careful reading of the English manuscript of Vol. I. The electronic files of the manuscripts were edited by Dr. H. Shen and Dr. X. L¨u. The research of J. Chu’s group as is presented in this book was supported by the National Natural Science Foundation of China, the Ministry of Science and Technology of the People’s Republic of China, the Chinese Academy of Science, and the Science and Technology Commission of the Shanghai Municipality. March 2009

Junhao Chu Arden Sher

Contents

1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Impurities and Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.1 Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.2 Chemical Analysis of Impurity Defects and their Conductivity Modifications . . . . . . . . . . . . . . . . . . . . . . . 10 2.1.3 Theoretical Estimation Method for Impurity Levels . . . . . . . 14 2.1.4 Doping Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 2.1.5 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.2 Shallow Impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 2.2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 2.2.2 Shallow Donor Impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.2.3 Shallow Acceptor Impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 2.3 Deep Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 2.3.1 Deep Level Transient Spectroscopy of HgCdTe . . . . . . . . . . . . 61 2.3.2 Deep Level Admittance Spectroscopy of HgCdTe . . . . . . . . . 69 2.3.3 Frequency Swept Conductance Spectroscopy . . . . . . . . . . . . . . 75 2.4 Resonant Defect States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 2.4.1 Capacitance Spectroscopy of Resonant Defect States . . . . . . 80 2.4.2 Theoretical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 2.4.3 Resonant States of Cation Substitutional Impurities . . . . . . . 85 2.5 Photoluminescence Spectroscopy of Impurities and Defects. . . . . . . 87 2.5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 2.5.2 Theoretical Background for Photoluminescence . . . . . . . . . . . 89 2.5.3 Infrared PL from an Sb-Doped HgCdTe . . . . . . . . . . . . . . . . . . . .103 2.5.4 Infrared PL in As-doped HgCdTe Epilayers . . . . . . . . . . . . . . . .108 2.5.5 Behavior of Fe as an Impurity in HgCdTe . . . . . . . . . . . . . . . . . .113 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .119

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Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125 3.1 Recombination Mechanisms and Life Times . . . . . . . . . . . . . . . . . . . . . . .125 3.1.1 Recombination Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125 3.1.2 The Continuity Equation and Lifetimes . . . . . . . . . . . . . . . . . . . . .127 3.1.3 The Principle Recombination Mechanisms and the Resulting Lifetimes of HgCdTe. . . . . . . . . . . . . . . . . . . . .128 3.2 Auger Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .134 3.2.1 The Types of Auger Recombination . . . . . . . . . . . . . . . . . . . . . . . .134 3.2.2 Auger Lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135 3.3 Shockley–Read Recombination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144 3.3.1 Single-Level Recombination Center . . . . . . . . . . . . . . . . . . . . . . . .144 3.3.2 General Lifetime Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .148 3.4 Radiative Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .152 3.4.1 Radiative Recombination Processes in Semiconductors . . .152 3.4.2 Lifetime of Radiative Recombination . . . . . . . . . . . . . . . . . . . . . . .153 3.4.3 Radiative Recombination in p-Type HgCdTe Materials. . . .156 3.5 Lifetime Measurements of Minority Carriers . . . . . . . . . . . . . . . . . . . . . . .158 3.5.1 The Optical Modulation of Infrared Absorption Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .158 3.5.2 The Investigation of Minority Carriers Lifetimes in Semiconductors by Microwave Reflection. . . .169 3.5.3 The Application of Scanning Photoluminescence for Lifetime Uniformity Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .172 3.5.4 Experimental Investigation of Minority Carrier Lifetimes in Undoped and p-Type HgCdTe . . . . . . . .176 3.6 Surface Recombination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .183 3.6.1 The Effect of Surface Recombination . . . . . . . . . . . . . . . . . . . . . . .183 3.6.2 Surface Recombination Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188 3.6.3 The Effect of Fixed Surface Charge on the Performance of HgCdTe Photoconductive Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .190 Appendix 3.A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196 Appendix 3.A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196 Appendix 3.B Sandiford Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .197 Appendix 3.B Sandiford Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .197 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .199

4

Two-Dimensional Surface Electron Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .203 4.1 MIS Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .203 4.1.1 The Classical Theory of an MIS Device . . . . . . . . . . . . . . . . . . . .203 4.1.2 Quantum Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .209 4.2 A Theory That Models Subband Structures . . . . . . . . . . . . . . . . . . . . . . . . .211 4.2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .211 4.2.2 A Self-Consistent Calculational Model . . . . . . . . . . . . . . . . . . . . .214 4.3 Experimental Research on Subband Structures . . . . . . . . . . . . . . . . . . . . .222

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4.3.1

Quantum Capacitance Subband Structure Spectrum Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .222 4.3.2 Quantum Capacitance Spectrum in a Nonquantum Limit . .229 4.3.3 Experimental Research of Two-Dimensional Gases on the HgCdTe Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233 4.3.4 Experimental Research of a Two-Dimensional Electron Gas on an InSb Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . .238 4.4 Dispersion Relations and Landau Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . .242 4.4.1 Expressions for Dispersion Relations and Landau Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .242 4.4.2 Mixing of the Wave Functions and the Effective g Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .247 4.5 Surface Accumulation Layer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .252 4.5.1 Theoretical Model of n-HgCdTe Surface Accumulation Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .253 4.5.2 Theoretical Calculations for an n-HgCdTe Surface Accumulation Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .255 4.5.3 Experimental Results for n-HgCdTe Surface Accumulation Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .257 4.5.4 Results of an SdH Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . .258 4.6 Surfaces and Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .263 4.6.1 The Influence of Surface States on the Performance of HgCdTe Photoconductive Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .263 4.6.2 The Influence of the Surface on the Magneto-Resistance of HgCdTe Photoconductive Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .269 4.6.3 The Influence of Surfaces on the Magneto-Resistance Oscillations of HgCdTe Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .274 4.6.4 The Influence of the Surface on the Correlation Between Resistivity and Temperature for an HgCdTe Photoconductive Detector. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .276 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .278 5

Superlattice and Quantum Well . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .283 5.1 Semiconductor Low-Dimensional Structures . . . . . . . . . . . . . . . . . . . . . . .283 5.1.1 Band Dispersion Relation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .283 5.1.2 Density of States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .288 5.1.3 Optical Transitions and Selection Rules . . . . . . . . . . . . . . . . . . . .289 5.2 Band Structure Theory of Low-Dimensional Structures . . . . . . . . . . .292 5.2.1 Band Structure Theory of Bulk Semiconductors . . . . . . . . . . .292 5.2.2 Envelope Function Theory for Heterostructures . . . . . . . . . . . .296 5.2.3 Specific Features of Type III Heterostructures . . . . . . . . . . . . . .303

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5.3

Magnetotransport Theory of Two-Dimensional Systems . . . . . . . . . . .306 5.3.1 Two-Dimensional Electron Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . .306 5.3.2 Classical Transport Theory: The Drude Model . . . . . . . . . . . . .308 5.3.3 Landau Levels in a Perpendicular Magnetic Field. . . . . . . . . .309 5.3.4 The Broadening of the Landau Levels . . . . . . . . . . . . . . . . . . . . . .312 5.3.5 Shubnikov-de Haas Oscillations of a 2DEG . . . . . . . . . . . . . . . .313 5.3.6 Quantum Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .315 5.4 Experimental Results on HgTe/HgCdTe Superlattices and QWs . .321 5.4.1 Optical Transitions of HgTe/HgCdTe Superlattices and Quantum Wells . . . . . . . . . . . . . . . . . . . . . . . . . . .321 5.4.2 Typical SdH Oscillations and the Quantum Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .325 5.4.3 Rashba Spin–Orbit Interaction in n-Type HgTe Quantum Wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .328 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .334 6

Devices Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .341 6.1 HgCdTe Photoconductive Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .341 6.1.1 Brief Introduction to Photoconductive Device Theory . . . . .341 6.1.2 Device Performance Characterization Parameters . . . . . . . . . .345 6.1.3 Noise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .348 6.1.4 The Impact of Carrier Drift and Diffusion on Photoconductive Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .356 6.2 Photovoltaic Infrared Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .360 6.2.1 Introduction to Photovoltaic Devices. . . . . . . . . . . . . . . . . . . . . . . .360 6.2.2 Current-Voltage Characteristic for p–n Junction Photodiodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .363 6.2.3 The Photocurrent in a p–n Junction . . . . . . . . . . . . . . . . . . . . . . . . .377 6.2.4 Noise Mechanisms in Photovoltaic Infrared Detectors . . . . .381 6.2.5 Responsivity, Noise Equivalent Power and Detectivity . . . .384 6.3 Metal-Insulator-Semiconductor Infrared Detectors . . . . . . . . . . . . . . . . .389 6.3.1 MIS Infrared Detector Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . .389 6.3.2 The Dark Current in MIS Devices. . . . . . . . . . . . . . . . . . . . . . . . . . .394 6.4 Low-Dimensional Infrared Detectors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .400 6.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .400 6.4.2 Basic Principles of QW Infrared Photodetectors . . . . . . . . . . .403 6.4.3 Bound-to-Continuum State Transition QW Infrared Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .408 6.4.4 Miniband Superlattice QWlPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .415 6.4.5 Multiwavelength QW Infrared Detectors . . . . . . . . . . . . . . . . . . .417 6.4.6 Quantum-Dots Infrared Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . .419 6.5 Low-Dimensional Semiconductor Infrared Lasers . . . . . . . . . . . . . . . . .427 6.5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .427 6.5.2 Basics of Intersubband Cascade Lasers . . . . . . . . . . . . . . . . . . . . .429 6.5.3 Basic Structures of Intersubband Cascade Lasers . . . . . . . . . .433 6.5.4 Antimony Based Semiconductor Mid-Infrared Lasers . . . . .446

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6.5.5 Interband Cascade Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .449 6.5.6 Applications of Quantum Cascade Lasers . . . . . . . . . . . . . . . . . .455 6.6 Single-Photon Infrared Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .456 6.6.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .456 6.6.2 Fundamentals of an APD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .458 6.6.3 The Basic Structure of an APD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .464 6.6.4 Fundamentals of a Single-Photon Avalanche Diode (SPAD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .468 6.6.5 Examples of Single-Photon Infrared Detectors . . . . . . . . . . . . .474 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .480 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .489 I Various Quantities for Hg1x Cdx Te . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .489 1 Energy band gap Eg (eV) from (A.1) (Appendix Part II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .489 2 Wavelengths corresponding to energy gaps Eg .m/ . . . . .492 3 Peak-wavelengths of the photo-conductive response peak and the cut-off wavelengths co .m/ for samples with a thickness d D 10 m (from (A.2) to (A.3) in Appendix Part II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .494 4 Intrinsic carrier concentrations ni .cm3 / (from (A.4) in Appendix Part II) . . . . . . . . . . . . . . . . . . . . . . . . . . . .497 5 Electron effective masses at the bottom of conduction band m0 =m0 (from (A.12) in Appendix Part II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .498 II Some Formulas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .500 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .503

Chapter 1

Introduction

This is the second volume of a two-volume set describing the properties of narrow gap semiconductors and devices made from them. The first volume entitled “Physics and Properties of Narrow Gap Semiconductors” sets the stage for the present volume. In the first volume most of the fundamental properties of the narrow gap semiconductors, both theoretical and experimental, are developed, while in this volume these fundamental properties are extended to those more specific to device physics. This volume contains extensive reviews of defects in semiconductors, recombination mechanisms, two-dimensional surface gases formed in inversion layers, superlattices and quantum wells, and a variety of devices. Chapter 2 begins with a theoretical study of defects, shallow and deep impurity states as well as native point defects, and continues with an extensive treatment of experimental methods to characterize these states. The methods deal with defect concentrations resulting from different fabrication strategies, and their characteristic states in the band gap and those that resonate in the conduction and valence bands. The theory ranges from Green function methods based on a tight binding model to more accurate ones based on density functional theory with full potentials in the linearized muffin tin orbital approximation. Experimental methods that are treated to determine defect concentrations and their energy states include neutron, electron, and X-ray scattering; chemical techniques; and capacitance voltage, deep level transient, admittance, transmission, photoluminescence, and frequency swept conductance spectroscopes. These methods yield not only defect densities and their states, but also their state band widths, and their impact on carrier populations and lifetimes. Chapter 3 focuses on recombination mechanisms. The mechanisms treated include both those that are intrinsic (Auger and radiative), and extrinsic (trap assisted). Auger recombination arises from two principal mechanisms, denoted Auger 1 and 7. Auger 1 is a mechanism in which an electron and a hole recombine with the excess energy taken up by a second electron in the conduction band being excited into a higher state. Auger 7 is a process in which the recombination energy excites an electron from the light hole band into an empty state in the heavy hole band. This process is more important in p-type material, while Auger 1 is more important in n-type material. Radiative recombination is one in which an electron and hole recombine with

J. Chu and A. Sher, Device Physics of Narrow Gap Semiconductors, Microdevices, c Springer Science+Business Media, LLC 2010 DOI 10.1007/978-1-4419-1040-0 1, 

1

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1 Introduction

the excess energy taken up by the emission of a phonon. If the material has a direct band gap the process can proceed by a vertical process since photons have almost no momentum, but for an indirect band gap material the process must be accomplished with the assistance of a phonon to conserve both energy and momentum. Trap-assisted recombination is a theory treated by several people but the one most quoted is Shockley-Read recombination theory. The simplest version of this theory deals with a situation where there is a trap with a state in the band gap that is neutral when it is empty and can accept a single electron so it is negative when full. The theory starts from two continuity equations, one for the electrons and the other for the holes. This provides two equations in three unknowns, the electron, the hole, and the trap populations. In the Shockley-Read treatment they make the so-called steady state approximation in which they assume that the rate at which the electron and hole populations change is the same. This provides the third equation. With this approximation, the problem is reduced to one that has a single relaxation time that depends on the net trap population, the trap energy, the Fermi level, and the temperature. This theory has been used extensively by many authors to treat a variety of problems, so while it is an unjustified approximation it appears repeatedly throughout the reminder of the book. The third equation in a proper treatment, done here for the first time, is the charge neutrality condition. It along with the two continuity equations forms a set of nonlinear first-order differential equations that can be reformulated as a second-order nonlinear differential equation. The solutions to this equation have at least two exponentials with different relaxation times. Special cases are treated that display details clearly differing from those of the Shockley-Read approximate solutions. In view of this development, while it is not done in this book, much of the literature of trap-assisted recombination needs to be reformulated. This chapter goes on to prescribe many experimental methods to measure the various relaxation processes along with results. The measurement methods include: optical modulation and infrared absorption, microwave reflection following pulsed irradiation, decay of the photoconductivity, scanning photoconductivity to measure the spatial variation of the decay, and the temperature dependence of these methods to separate out the Auger, radiative and trap-assisted contributions to the decay. Chapter 3 deals with two-dimensional electron gases (2DEG) systems. These 2DEG systems occur when the bias voltages in MIS structures are such that they are in inversion, or even sometimes when they are in depletion. Then the potential adjacent to the insulator has a sharp variation that allows quantum states to form in the resulting potential well. Fixed charge in the insulator as well as slow and fast defect states can effect these quantum states. All these possibilities are captured in a theory of these quantum states. The theory of these 2DEG’s reveals their energy levels and populations as functions of the spatial variation of the well, the effective Fermi level, and the temperature. Experimental methods to measure the responses of these states on both n- and p-type samples include: C-V spectroscopy, SdH oscillations as a function of magnetic field orientation and also the Fourier transform of the oscillations, and cyclotron resonance. These measurements reveal the ground state and some excited state energies of the 2DEG, as well as their populations, and

1 Introduction

3

broadening mechanisms. Finally there are experiments to explore the impact these effects have on various devices, particularly those that depend on conductivity or magnetoresistance. Chapter 4 delves into effects arising from superlattices and quantum wells. The band structures of superlattices composed of multiple layers of low-dimensional materials depend on boundary conditions derived from envelope functions. The theory treats interface states among materials that do not have a lattice match as well as those that do. It also deals with superlattices in which at least one material has an inverted band structure, e.g. HgTe/CdTe. The influence of the presence of a magnetic field is also treated. Once again a collection of experiments to explore the properties of these materials are presented with an emphasis on the HgTe/CdTe superlattice. Finally there is a section devoted to metal/semiconductor interfaces with blocking contacts. The quantum Hall effect is also discussed in this section. Finally, Chapter 5 begins by treating a collection of homo- and/or heterojunction semiconductor alloy-based infrared detector devices ranging from photoconductors to various photodiodes. Expressions for the responsivity (the ratio of the signal voltage to the incident radiative power), and the detectivity (the ratio of the signal to noise voltages divided by the incident optical power, times a normalization factor consisting of the square root of the product of the device area and the noise band width) are deduced. Several parameters important to device performance are explored in some detail. These include the quantum efficiency (the ratio of the incident photon flux to that actually absorbed by the device), all the different noise sources in the various operating modes, and the operating temperature. Once again the results of numerous experiments to explore these properties are presented. Then a section is devoted to metal-insulator-semiconductor (MIS) structured devices. Now the metal/semiconductor blocking contact Schottky barrier replaces the p-n junction of the diode. This introduces some modifications to the factors influencing the operating mode analysis, but they are minor. Once again both theory and experiments are presented. The next sections treats quantum well infrared photodetector (QWIP) based devices as well as other QW structures. These devices consist of a periodic set of QWs each imbedded in barrier layers. The quantum wells contain states trapped in them. There are numerous operating modes that have been tried. Some function by absorbing photons that excite electrons from a bound state into the continuum where they are collected because of an externally applied field. Others function by photon absorption exciting electrons from one bound state to another bound state from which they progressively tunnel under the influence of an external field through a succession of excited bound states until they are collected. There are two classes of QWIP materials, those with a small conduction band offset, e.g., GaAs/AlGaAs and InGaAs/AlGaAs, and those with a large conduction band offset, e.g., InAs/InGaSb and InAs/InAsSb. But for both classes because of the selection rules for the absorption among two-dimensional quantum wells, only the component of the incident radiation that is parallel to the interface is absorbed. This restricts the incident optical system, and along with a requirement for low-temperature operation severely limits the quantum efficiency of QWIPs. To some extent this failing is mitigated

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1 Introduction

by quantum dots (QD) based detectors. Because QDs have three dimensional wells, selections rules allow normal incident photons to be absorbed, and while they are harder to fabricate they function better than QWIPs. A subsequent section deals with quantum cascade lasers (QCL). They constitute the first semiconductor lasers that are tunable over a wide range of wavelengths from the near to the far infrared. The QCLs consist of a sequence of layers each containing an injector and a QW. The large tunable range is accomplished by changing the QW widths and/or their barrier heights. The materials used in QCLs are III-V compound semiconductor alloys grown on GaAs or InP substrates. A number of different operating modes have been devised and tested that feature different alloys and structures. A detailed evaluation of the benefits and disadvantages of these modes is presented. The final section treats single-photon detectors ranging from traditional photomultiplier tubes (PMT) that operate in the visible at room temperature, to QD single-photon transistor (SPT) devices that operate in the FIR (175–210 m) at  0:04 K. The general designation of this class of devices is avalanche photodiodes (APD). The fundamental mechanism involved is avalanche gain produced from the primary photoexcited electro/hole pair by further exciting them into hot electrons or holes in a high electric field. Not only the signal but also the noise mechanisms are treated. There are many modes of APDs that have been built from several materials, including Si, Ge, and InGaAs/InP, and tested in the NIR. Some have been demonstrated to operate at room temperature but function better at 77 K. Single-photon avalanche diodes (SPAD) devices are called out for special attention. Coupled with quenching circuits these devices detect single photon events with quenching times of a few nanoseconds. Thus, they are suitable for digital communications applications. Finally, a new class of single-electron transistor (SET) APD devices made from QDs in a high magnetic field has been demonstrated. The absorption is due to transitions among Landau levels. They operate at very low temperatures ( 0:04 K), and function in the FIR (175–210 m) in circuits that respond at frequencies above 10 MHz. In sum, we hope that this detailed discussion and review of the extensive literature on the properties and device physics of narrow gap semiconductors fills an important need. The literature on this subject as reviewed here is extensive, and we believe the addition of some papers, previously published only in Chinese, adds important aspects.

Chapter 2

Impurities and Defects

Investigating impurities and defects for any semiconductor material is an important topic. Much research has been devoted to impurity and defect states in wide-gap semiconductor materials. For the pseudobinary semiconductor alloy HgCdTe (mercury cadmium tellurium (MCT)), which is a good material for preparing infrared detectors, the investigation of its defects has a special significance. The behavior of impurities and defects in HgCdTe has been discussed in many papers in recent years. However, the research on impurities and defects of HgCdTe has encountered considerably more complexity and difficulty than that encountered in other semiconductors because of its narrow band gap, the low conduction band effective mass, the ease with which Hg vacancies are formed, and complex with other native point defects and impurities. Despite these difficulties, research in recent years have provided a basic description of impurities and defects, and their diffusion and photoelectric behavior in HgCdTe. For the narrow gap semiconductor material HgCdTe, we need to know which kind of impurities and defects exist in the material, their chemical composition and electrical activity, if they are p-type or n-type, the magnitude of the impurity concentration, the ionization energies of these defects, their impact on electrical and optical properties, how to experimentally observe their properties, and how to theoretically analyze their properties.

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects 2.1.1 Defects One of the major differences between real crystals and ideal crystals is that, in a real crystal, there are many defective areas where the regular arrangement of atoms has been destroyed. Defects result from many factors such as impurity atoms, growth aberrations, e.g., dislocations or planar defects, point defects resulting in an excess or a deficiency of some elements in the compound. The primary defects in an HgCdTe (Swink and Brau 1970; Yu 1976; Bye 1979; Mirsky and Shechtman 1980; J. Chu and A. Sher, Device Physics of Narrow Gap Semiconductors, Microdevices, c Springer Science+Business Media, LLC 2010 DOI 10.1007/978-1-4419-1040-0 2, 

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Wang et al. 1984; Cheung 1985; Cole et al. 1985; Bubulac et al. 1985; Cai 1986; Kurilo and Kuchma 1982; Datsenko et al. 1985; Rosemeier 1983; Petrov and Gareeva 1988; Schaake 1988; Yu et al. 1990; Chen 1990; Dean et al. 1991; Shin et al. 1991; Wang et al. 1992; Yang 1988) mainly derive from (1) intrinsic point defects, e.g., vacancies, interstitial atoms, antisites, and complexes of these defects; (2) impurities; (3) multidimensional structural defects, such as dislocation, grain boundaries, and strains. Thus the geometry of lattice defects includes point, line, planar and bulk defects. Because of a Maxwell distribution of atomic kinetic energies during crystal growth, some atoms always have a sufficient kinetic energy to leave lattice sites and be excited into “interstitial” positions to create a “vacancy–interstitial” pair. This pair can either be bound or unbound. When it is unbound it can be treated as the “evaporation” of an atom from a lattice site into a remote interstitial position. This special defect type is called a “Frenkel” defect. Now we turn to another kind of defect. During growth or annealing “Holes” may form on the surface of crystal and then diffuse into the interior of crystal. This kind of defect is called “Schottky” defect. It is the absence of an atom on a lattice site with the extra atom in the vapor phase. Thus for example, on the surface of a HgCdTe crystal, a Hg atom may evaporate leaving a VHg on the surface which then diffuses into the interior of crystal, to form a “Schottky” defect. There is also the possibility that the extra atom remains bound on the surface to cause the effective thermal expansion coefficient to be larger than otherwise expected. Both “Frenkel” and “Schottky” defects are caused by thermal motion within the crystal lattice. They are called thermally induced defects. There are many other thermally induced native point defects besides Frenkel and Schottky defects but these two are given special attention because they are so common. The densities of thermally induced defects are decided by the temperature of crystal and the formation energies of defects. Let UF denote the formation energy of a Frenkel defect, the work required to excite the atom from a lattice site into a remote interstitial position. In general there are a number of nonequivalent interstitial sites in the lattice, but usually one type of site has a much lower value of UF than the others. This is the site one identifies with the Frenkel defect. Let N and N 0 be respectively the number of lattice sites and interstitials. Suppose at a temperature T , n atoms have been excited from lattice sites to interstitial position to form a vacancy interstitial pair. If under this condition the system is in equilibrium there will be a increase in the entropy. The system entropy S can be written as: S D kB .ln P 0 C ln P /

(2.1)

where kB is the Boltzmann constant, P 0 is the number of n atoms distributed among the N 0 interstitial positions, and P is the number of n vacancies distributed among the N lattice sites: P0 D

N 0Š ; .N 0  n/ŠnŠ

(2.2)

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

P D

NŠ : .N  n/ŠnŠ

7

(2.3)

Substituting (2.2) and (2.3) into (2.1), and using Stirling’s formula (for a large value of x, then ln xŠ Š x.ln x  1//, we get: S D kB fŒN ln N  .N  n/ ln.N  n/  n ln n CN 0 ln N 0  .N 0  n/ ln.N 0  n/  n ln ng

(2.4)

Also atoms jumping into interstitial sites leads to an increase of the internal energy of crystal lattice: W D nUF (2.5) The thermal equilibrium condition occurs when the free energy F D W  T S is a minimum as a function of n: .N  n/.N 0  n/ @F D U  kB T ln D 0: @n n2

(2.6)

This gives the result:   p UF 0 n D .N  n/.N  n/ exp  : 2kB T Because both N  n and N 0  n, (2.7) can be written as:   p UF 0 : n D N N exp  2kB T

(2.7)

(2.8)

The factor of 1/2 in the exponent in (2.8) is due to the existence simultaneously of two kinds of defects in the crystal, interstitials and vacancies. Similarly, we can analyze of the number of Schottky defects, with the extra atom in the vapor phase, obtaining:   US n D N exp  ; (2.9) kB T where Us is the formation energy of a Schottky defect. Generally speaking, the formation energy of defect is temperature dependent. Assuming the formation energies depend linearly on the temperature, then we find: UF D UF0  T and

@.UF / D UF0  ˛T; @T

(2.10)

@.US / D US0  ˇT; (2.11) @T where UF0 and US0 are the formation energies of defects at absolute zero, and ˛ and ˇ are constants. US D US0  T

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2 Impurities and Defects

Substituting (2.10) and (2.11) into the expression for n, leads to the results:

and

  p UF ; n D BF N N 0 exp  2kB T

(2.12)

  US n D BS N exp  : kB T

(2.13)

The values of BF and BS can be approximated by fits to experiments. For all crystals, both BF and BS lie in the range 2–50. For HgCdTe crystals, F defects and/or S defects form under different annealing conditions. Besides thermal defects, there is another class of defects, irradiation-induced defects. When a high-speed particle such as a neutron, an ˛ particle, deuteron, fragments of nuclear fission,  radiation, a high-energy electron, a high-energy ion, or high-energy laser irradiates a crystal, it induces structural failures mostly in the form of “Frenkel” defects. When for example,  radiation irradiates the crystal, secondary photoelectrons and Compton electrons are produced which in turn induce structural defects. These kinds of crystal defects generated by irradiation are named irradiation defects. Irradiation defects are different from thermal defects. After irradiation, irradiation-induced defects are unstable and the crystal is not in thermodynamic equilibrium. When a crystal is annealed after irradiation, many irradiation-induced defects will diffuse quickly to recombine. When a massive neutral particle or charged high-speed particle irradiates a crystal, elastic collisions will take place between the high-speed incident particle and the atomic nuclei of the crystal. High-speed incident particles will cause the electrons bound in atoms of the crystal to be excited and to ionize. Also, an incident highspeed particle can induce a nuclear reaction leading to the activation of some atoms within crystal. These atoms will become impurity centers. However at lower incident energies in semi-conductor crystals, the excitation and ionization of the valance electrons are most prevalent. When an elastic collision between a high-speed particle and the atoms of a crystal takes place, elastic waves will form in the crystal to transform energy into the thermal motion energy of the atoms. Ultimately this results in a structural failure of the crystal. If the energy of the atoms at a lattice point exceeds a critical value Ud of the formation energy of a defect in the crystal, it will result in the structural failure of crystal lattice. Generally speaking, Ud needs to be two or three times that required for atoms go from the lattice to an interstitial site. Because the binding energy of most crystal atoms is 10 eV, the value of Ud is about 25 eV. So for an irradiated crystal, only those atoms with the energy U  Ud will form a Frenkel defect. Now we introduce a kinetic energy parameter " related to the kinetic energy of a moving particle: m E; (2.14) "D M1 where m is the electron mass, M1 the mass of the moving particle, E the energy of the moving particle, and " is the energy of an electron that has the same speed as

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

9

the moving particle. When " >> "i where "i is the excitation energy of a valence electron, the majority of the energy of the incident moving particle will be expend in the processes of excitation and increased ionization of the lattice ions, with little of the energy expend in elastic collisions. If the values of the parameter " approaches "i , the processes of excitation and ionization become difficult and only elastic collisions can take place, still resulting in the creation of elastic waves and structural defects. In an elastic impact process, there is approximately a proportional relation between the incident energy of the high-speed particle that results in a structure defect, and the energy consumed in the crystal. This proportional relation depends on the magnitude of the incident particle energy and properties of crystal. When an elastic impact between an incident particle occurs in a crystal, the energy loss per unit distance can be written as (Jones 1934; Mott and Jones 1936):  

dE dx

 D c

2Z12 Z22 e 4 N0 E ln  ; M2 v2 E

(2.15)

where Z1 and Z2 are the atomic number of the moving particle and a static lattice particle, respectively, N0 is the density of atoms in the crystal, v the velocity of the moving particle, E the energy of the moving particle, e the electron charge, M2 the mass of the static particle, and E  is given by the following expression: 2 mM  1 R; E  D 0:618 Z12=3 C Z21=3 42

(2.16)

where R is the Rydberg constant which is equal to 13.6 eV and  the reduced mass between the moving particle and the static particle. Similarly, the energy expended by the high-speed particle to form structural defects per unit distance can be written as:   2Z12 Z22 e 4 N0 dE E42  D ln : (2.17) 2 dx defect M2 v Ud M1 M2 Then the ratio of the energy to form structural defects to the total energy lost is:     dE E 42 ln dx defect Ud M1 M2  D  : (2.18) E dE ln  E dx c This ratio is about 0.5 for most crystals. According to (2.15), (2.17), and (2.18), we can determine approximately the factors related to forming irradiation-induced defects in crystals. These factors differ from each other for different crystals, and are related to the atomic mass of the crystal. Jones (1934) deduced the energy threshold for forming irradiation-induced defects in crystals with different atomic masses (see Table 2.1).

10 Table 2.1 The energy threshold of a high-speed particle for forming irradiation defects in crystals with different atomic masses

2 Impurities and Defects Crystal atom Atomic mass Neutron-atom (eV) Electron- ray (MeV) ˛ particle (eV) Nuclear fission chip

10 75 0.10 31 85

50 325 0.41 91 30

100 638 0.65 169 25

200 1,263 1.10 325 27

The density N of defects induced by high-speed incident particles irradiating a crystal can be written as:     E 42 m 1 M1 3 "t C ln ; (2.19) E  10 N D 2Ud m M1 Ud M1 M2 where the physical meaning of every parameter has been given above. Although the above equations are based on a relatively simplified model, they still can be employed as an approximate reference for analyzing the formation of irradiation defects in narrow gap semiconductor materials. In the discussion above, we have emphasized the thermal defects and irradiation defects, but in real semiconductors, the most common defect is an impurity. Impurities derived from elements differing from those on the crystal also modify the periodicity of crystal lattice and change the physical properties of crystal. Impurities can have a great influence on the electrical and optical properties of semiconductors. Impurity atoms can become donors or acceptors which influence the conductivity of the crystal. They can form trapping centers or recombination centers which will influence the lifetime of minority carriers and so influence the electrical and optical properties of a crystal.

2.1.2 Chemical Analysis of Impurity Defects and their Conductivity Modifications The technology involved in material growth and device fabrication often introduces impurity defects into the material. The states of these impurities always determine device characteristics. So, it is essential to understand the behavior of impurity defects. Accordingly, impurity defect states in a crystal lattice can be divided into shallow energy level, deep energy level, and resonant impurity defect states. Also they can be divided into donors, acceptors, and traps. Each kind of defect will serve as a scattering and/or a recombination center during transport to decrease the mobility and lifetime of carriers. So, device performance will be influenced. To prepare p-type, n-type, or p–n junctions in HgCdTe material, it is usually doped intentionally. We can add the impurities into the material directly in the growth process, make impurities diffuse into the material in a heat treatment process, or employ ion implantation. In the case where the material is unintentionally doped, the defects are either native point defects or residual impurities. People generally

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

11

employ “7N ” material (impurity densities <107 cm3 / to prepare HgCdTe devices. However, despite growers best efforts impurities still exist in the grown crystals in sufficient numbers to influence the properties of HgCdTe crystals (Pratt et al. 1986; Shen et al. 1980). Analyzing the relation between the impurity content, after purification, in the elemental materials used to prepare HgCdTe bulk crystal, and the ones in the grown bulk crystals indicates that the impurity density is almost the same. Generally speaking, the impurities found in HgCdTe bulk crystal are mostly derived from the elemental Te, Cd, and Hg materials. However, when HgCdTe bulk material is grown, the type and density of impurities also will be influenced by the quartz tube in which it is grown because it contains Al, Te, Ca, Mg, Ti, Cu, and B impurities. Most impurities in HgCdTe crystals are electrically active. Some impurities that are not electrically active still induce deep levels in the band gap and as a consequence will reduce the lifetime of minority carriers. Therefore, in the case of unintentionally doping, the content must be limited not just for certain specified impurities but for all of them. Theoretically, we can judge if an impurity is an acceptor or a donor in a HgCdTe semiconductor sample based on the atomic number of the impurity, its group number in the periodic table of elements and the sublattice on which it resides. Table 2.2 gives the results. In fact, not all of the impurity elements listed in Table 2.2 can be activated in HgCdTe. To observe the electrical activity of a particular impurity element in HgCdTe, it can be intentionally doped into the material. The carrier concentration of sample then can be determined by measuring the Hall coefficient of the sample. Then the doping concentration can be obtained from atomic absorption spectrometry. Knowing carrier concentration and doping concentration, we can find the degree of electrical activity as a function of temperature of this kind of impurity. Many authors have carefully investigated the degree of electrical activity for many kinds of impurity elements. The results indicate that the elements In, I, Cl, Al, and Si are definitely donors, and the elements P, As, and Sb, are amphoteric being donors if substituted on the cation sublattice and acceptors on the anion sublattice, while the electrical properties of Li, Cu, and Ag are definitely acceptors. Now we will discuss issues related to donor impurities. For example, in Hg1x Cdx Te (x D 0:20) crystals doped with In are n-type. The carrier concentration Table 2.2 Impurity elements their possible roles on different sublattices and in interstitial positions

group

I

II

III

IV

V

Li Na K Cu Ag Au

Cd Hg

B Al Ga In Tl

C Si Ge Sn Pb Ti

N P As Sb Bi V

VI

VII

VIII

F Cl Br I Mn

Fe Ni

Possible role

Element

Te

12

2 Impurities and Defects

increases with an increase of the In concentration and the Hg partial pressure in a heat treatment process. The carrier concentration is proportional to the square root of the In doping concentration, and to the square root of the Hg pressure (Vydyanath 1991). Only a fraction of the In atoms doped into HgCdTe crystals behave as single donors when In atoms are heavily doped because In can combine with Te to form In2 Te3 (Vydyanath et al. 1981). However, In atom impurities are fast diffusers, their diffusion coefficient is about 5  1014 cm2 =Vs at 300 K (the activation energy is 11 eV) (Destefanis 1985). This limits the stability of p–n junctions formed from In doping. A p–n junction can be formed when In atoms are introduced into a p-type HgCdTe substrate by ion implantation. The electrically active n-type defects caused by irradiation damage can be eliminated in an annealing process. In this kind of process the junction depth is easy to control (Destefanis 1985, 1988; Gorshkov et al. 1984). As stated before, because the Hg–Te bond is weak, it is easy to form Hg vacancies. Therefore, people have been motivated to study the interactivity between Hg vacancies and other impurities. The In atom is a common impurity in HgCdTe. The In atom is trivalent, and when substituted for Hg and Cd it is donor. But in higher concentrations it becomes compensated. One of the potential reasons is that In combines with Te to form In2 Te3 . The other reason is that In forms In-vacancy pair. Hughes et al. have analyzed theoretically the possibility of forming an In-vacancy pair (Hughes et al. 1991). They conclude an inactive In-vacancy pair will form when the material is quenched from above 350 K down to room temperature. These Invacancy pairs can be eliminated if the material is annealed at the temperature of 160 K (Hughes et al. 1994) in an atmosphere with a high Hg partial pressure. In is an element widely used to obtain an n-type-doped HgCdTe material. It is a suitable element to dope bulk materials, as well as liquid phase epitaxy (LPE), molecular beam epitaxy (MBE), and MOCVD film materials. However, because it is a fast diffuser, the so-called memory effect in the process of doping in which the raw In material having adsorption on the wall of growth tube or reactor, diffuses into the prepared p-on-n junction to cause it to be graded (Gough et al. 1991; Easton et al. 1991). To mitigate this problem Maxey et al. (1991), Easton et al. (1991), and Murakami et al. (1993) turned to the element I as a dopant. The element I is a group VII element which when substituted on the Te sublattice is a donor. Because I has a relatively small diffusion coefficient very steep p-on-n junctions can be prepared. I has and very weak “memory” effect. The element I is an adequate dopant not only for inter-diffusion of multilayer films but also for direct growth of alloys. When the electron concentration of an I-doped Hg1x Cdx Te (x D 0:23) sample is between 51015 and 21018 cm3 at a temperature of 77 K about 20–100% of the I is activated as donors. The carrier mobility of an I-doped Hg1x Cdx Te (x D 0:23) sample is greater than that of the same sample doped with In at the temperature of 20 K. The activated I doping concentration in a HgCdTe crystal is related to the Hg pressure when diffusion doping is done. The higher the Hg pressure, the larger is the I doping concentration. The element I forms compounds of (Hg,Cd)I2 in a HgCdTe crystal, to limit its electrical activity (Vydyanath et al. 1981; Vydyanath and Kr¨oger 1982; Vydyanath 1991).

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

13

Elemental O is very active, and it is easily doped into HgCdTe crystals in the process of crystal growth. Because element O is a donor, the carrier concentration of an n-type HgCdTe crystal will increase when the concentration of O atoms is high. The O atoms derived from the walls of a quartz tube diffusing into a HgCdTe crystal can be obstructed when C atoms are deposited on the wall of quartz tube. Consequently, the carrier concentration of an n-type HgCdTe crystal will be decreased. Given this de-oxidation process the carrier concentration can be accurately controlled in the range of ˙1  1014 cm3 (Yoshikawa et al. 1985). Some electrical parameters of an n-type Hg0:7 Cd0:3 Te crystal at 77 K obtained by this method are as the follows: electron concentration 65  1013 cm3 , electron mobility 4  104 cm2 =Vs, a maximum minority carrier lifetime of 74 s. These results indicate that the O atom is an important background impurity donor for n-type HgCdTe crystals. Group V elemental impurities are amphoteric, acting as a donor when occupying the Hg and Cd cation sublattice, and acting as an acceptor when located on the Te anion sublattice. For example, the As atom can be doped into a HgCdTe crystal by high-temperature diffusion (Capper 1982) and ion implantation (Destefanis 1988; Baars et al. 1988; Wang 1989; Ryssel et al. 1980). In an ion implantation experiment, people found that As ions forms nonelectrically active charge compensation complexes that do not migrate easily in HgCdTe crystals. However, some inactive As atoms will be activated to be donor impurities when the material is annealed at 300 K, and to be acceptors when annealed above 400 K. In HgCdTe crystals, the electrical behavior of Sb atoms is similar to that of As atoms. The Sb atoms will be acceptors when occupying the Te sublattice and be donors when located on the Hg sublattice (Wang 1989). The electrical behavior of P atoms is relatively complex. The P atoms, when the sample is held at high Hg partial pressure, are located on interstitial positions or on the Te sublattice and become single acceptors. However, when the Hg partial pressure is low, the P atoms are located at on the cation sublattice and are single donors (Vydyanath 1990, 1991; Gorshkov et al. 1984). Next we discuss acceptor impurities. Cu atoms located on the cation sublattice are single acceptors in HgCdTe (Vydyanath et al. 1981; Gorshkov et al. 1984). Cu deposits in a cooling process when its concentration becomes high enough to reach saturation. Since Cu deposits always collect around the positions of extended defects, one can observe these defects in HgCdTe as they are Cu decorated. This method is destructive to materials. Later we will see that the Cu atoms are derived from the walls of the quartz tube during growth. When the Cu content is relatively high, it may become the most important background acceptor impurity. The elements P, As, Ag, and Sb are all p-type impurities in materials grown from the Hg-rich side of the existence curve, and their diffusion rates are relatively slow (Vydyanath et al. 1981, Vydyanath 1991; Gorshkov et al. 1984; Wang 1989; Ryssel et al. 1980). The elements P, As, and Sb have been used widely as the doping agents to manufacture HgCdTe photovoltaic devices. Previous research indicates that Sb-doped HgCdTe samples are more stable than the As-doped ones (Wang 1989; Capper et al. 1985).

14

2 Impurities and Defects

In HgCdTe crystals, Au atoms exhibit a low electrical activity, and almost do not change the carrier concentration or the minority carrier lifetime. Often only 3% of the Au are electrically active acceptors. But Au can be used to fabricate electrodes at temperatures below 150ı C (Capper 1982; Jones et al. 1983). Chu’s experimental results indicate that the concentration of Au acceptors can reach 1018 cm3 (Chu et al. 1992). They evaporated Au onto the surface of samples, then used a YAG laser to irradiate the sample, followed by annealing at a temperature of 250ı C for 20 h. After the Au impurities diffused into the samples, a CV measurement was done on the resulting metal–insulator–semiconductor (MIS) structure. They found that the concentration of acceptors increases as diffusion progresses, finally reaching levels of about 1018 cm3 . This indicates that Au exists in HgCdTe as an acceptor. For most of the elements, the doping concentration N and carrier concentration n lie close to the straight line N D n. However, the electrical activity of both Fe and Au are very low. For Fe and Au atoms with the concentrations of about 1017 cm3 , their corresponding excited carrier concentrations are only about 1015 cm3 . Furthermore, even when the concentrations of Fe and Au increase up to 1018 cm3 , the carrier concentrations are still 1015 cm3 , having saturated. The transition metal elements, such as Fe, though they show little electrical activity in a HgCdTe crystal, still can reduce the lifetime of the minority carriers markedly, and so are called “lifetime killers” (Capper 1982, 1991). In the preparation of the raw materials and subsequent growth of HgCdTe, extensive efforts are needed to control their impurity content. The electrical activity is different in Hg1x Cdx Te crystals with different compositions. For example, the electrical activity of the Cl atom is only several percent when the concentration is x < 0:3, while it is almost a 100% when x > 0:3. The As and Sb atoms behave similar to that of Cl atoms (Capper 1991). Approximately, the main group and the subgroup elements of group I and the main group elements of group V are acceptors; and the subgroup elements of group II, the main group elements of group III and VII are donors. Neutral impurities are relatively complex. For example, for elements of group IV, the element Si behaves as donor, while Ge, Sn, and Pb are neutral impurities, having a different behavior than that anticipated. The anticipated conductivity of impurity elements is almost consistent with those encountered in practical cases, but there are still some deviations. Table 2.3 lists the electrical behavior of 26 elements in HgCdTe crystals (Capper 1991).

2.1.3 Theoretical Estimation Method for Impurity Levels It is important to observe the ionization energy of impurity defects based on an understanding of their impact on the conductivity. There are some rough empirical expressions available to characterize the ionization energy of shallow impurities. For an n-type HgCdTe material, measurements of the Hall coefficient indicate that the ionization energy of a univalent donor is almost zero. For a p-type HgCdTe material, the measurements indicate that an acceptors ionization energy increases

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

15

Table 2.3 Electrical activity of impurities in HgCdTe crystals Practical case Element H Li Cu Ag Au Zn Hg B Al Ga In Si Ge Sn Pb P As Sb Bi O Cr F Cl Br I Fe Ni

Group IA IA IB IB IB IIB IIB IIIA IIIA IIIA IIIA IVA IVA IVA IVA VA VA VA VA VIA VIB VIIA VIIA VIIA VIIA VIII VIII

Anticipated behavior A(m) A(m) A(m) A(m) A(m) I(m)D(i) I(m)D(i) D(m) D(m) D(m) D(m) D(m)A(t) D(m)A(t) D(m)A(t) D(m)A(t) A(t) A(t) A(t) A(t) D(i)I(t) I(t) D(t) D(t) D(t) D(t) I(m)D(t) I(m)D(t)

SSR (Te)

II (Te)

LPE (Hg)

A A A A

A A

A A A I

D D D D D I I I I=A C A I=A C A I

D D D D D

D D D

LPE (Te) A A A

MOVPE (Hg)

D I D

MBE (Te)

A

A A A

I D D D D D?

D

D D? A A

MOVPE (Te)

I/D D D D

D D D

D I(A) I(A) I(A) I D

A A A

I I I/D

D/A D

D?

D D D

D

D

(D) (D) (D)

I I

A acceptor, donor, I inactive, .m/ D at the lattice point of metal, .t/ D at the lattice point of Te, .i/ D at interstitial position, I.A/ D impurity that needs to be activated by annealing at hightemperature, I=D and D=A D different results obtained from that impurities are activated under different conditions, .D/ D donor in CdTe buffer layer, II D ion implantation.

proportional to the composition x, and decreases proportional to the cube root of the acceptor concentration, Na1=3 . In the range, 0:2 < x < 0:24, the ionization energy can be written as the following empirical formulas (Capper 1991): A. When Na is in the range of 2:5–3:5  1017 cm3 Ea D 91x C 2:66  1:42  105 Na1=3 .unintentionally doped/;

(2.20)

B. When Na is in the range of 0:8–2:5  1017 cm3 Ea D 42x C 1:36  1:40  105 Na1=3 .intentionally doped/:

(2.21)

16

2 Impurities and Defects

The energy level of impurity defects also can be estimated theoretically. For the group II–VI compound semiconductor HgCdTe, the anion Te has valance 6, and the cations Hg and Cd have valance 2. Thus according the simple rules, if group VII elements are substituted on the anion sublattice they are donors, and group V elements are acceptors. Similarly, if group III elements are substituted on the cation sublattice they are donors, and group I elements are acceptors. Generally, group V elements substituted on the cation sublattice are also donors and group III elements substituted on the anion sublattice are acceptors. The energy released to the conduction band by a donor atom is called the ionization energy Ei . The electron concentration n of the conduction band can be obtained from Hall coefficient measurements. The electron concentration of the conduction band is proportional to exp.Ei =kT /. So Ei can be obtained from the slope of the measured curve, ln.n/  1=T . However, for narrow gap semiconductors, the donor ionization energy Ei to the conduction band is very small. So the error is relatively large when Ei is determined by this method. The ionization energy of any impurity in a semiconductor with shallow ionization energy can be calculated in a simple effective mass theory. Generally, for a semiconductor with a large dielectric constant and a small effective mass, the binding energy of a shallow donor impurity can be calculated by means of the effective mass approximation (EMA) method. The physical picture behind this method is that, a crystal is looked upon as continuous dielectric medium, a carrier moves like free particle in this dielectric, the effective mass related to the energy band replaces the free particle mass, and the binding potential of the impurity is controlled by the dielectric constant of the host lattice. Assuming that the distance between an impurity ion and a bound electron is r, and ".0/ is the static dielectric constant of crystal, we get the interaction potential between single positive charge and the electron located at the displacement r: V .r/ D 

e2 : 4".0/r

(2.22)

The electron can be regarded as one having an effective mass m that is moving in a potential V .r/. This hydrogen atom-like model can then be solved to deduce the ground state energy or equivalently the ionization energy. The following equation is obtained in the EMA:   e2 „2 2 .r/ D E .r/: (2.23)   rr  2m 4".0/r @2 Because the potential is spherically symmetrical, rr2 ) . The eigenvalues of @r 2 (2.23) are: R (2.24) En D  2 ; n where m e 4 m 1 RH ; D (2.25) R D 2 2„ Œ4".0/2 m0 "2 .0/

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

17

and R is called the equivalent Rydberg energy, with RH being the Rydberg energy of a hydrogen atom equal to 13.6 meV. n is an integer, so (2.24) gives a series of binding energy levels with the ground state being R . Therefore the ionization energy is, Ei D R . For silicon, the effective mass is m D 0:2m0 without considering the anisotropy of mass tensor, and the value of " is 12, so one gets En D 0:0181=n2 .eV/. Then the binding energy of the ground state n D 1 is E1 D 0:0181 eV D Ei . For Hg1x Cdx Te.x D 0:4/, with m D 0:04m0 , ".0/ D 15, then En D 0:0024=n2 .eV/ or Ei D 2:4 meV. For the heavy hole band, m D 0:55m0 , then En D 0:0033=n2 .eV/ or Eihh D 3:3 meV. For Hg1x Cdx Te.x D 0:2/, with m D 0:01m0 , ".0/ D 17:5, then we find Ei D 0:5 meV. For an electron bound to an impurity center, the extent of spatial wave functions radius, an , corresponding to “the nth Bohr orbit radius” of a hydrogen-like wave function is: n2 ".0/ (2.26) an D a0 ; .m =m0 / where a0 is the first Bohr orbit radius of hydrogen, a0 D 0:53  108 cm. For a ˚ and for a donor in germanium, a1 D 80 A. ˚ group V donor in silicon, a1 D 30 A,  ˚ For donors in HgCdTe, if m =m0 D 0:04, " D 15, then a1 D 198 A. Therefore, when an impurity concentration is very high, the electron wave functions bound to impurities will overlap. If an impurity is located in an interstitial rather than a substitutional position, its energy levels may not follow the simple hydrogenic effective mass model of a shallow impurity. Its energy levels may involve an impurity complex with its wave functions overlapping neighboring atoms. Strictly speaking, even for a substitutional impurity, its ground state wave function may be localized, so its binding energy can not be calculated simply by using the effective mass model. In fact strictly speaking, the electric potential of an impurities core can not be regarded as that of point charge, and more complete approximation divides the region close to impurity into two parts, an interior and an exterior region. In the exterior region, r > rc , where rc is the same order of magnitude as the distance to a nearest neighbor, an effective mass model is approximately correct and the potential energy can be regarded as e 2 ="r. In the interior region where, r < rc , the potential energy of the impurities atomic core can be regarded as a ı-function potential well. In this approximation the depth of the ı-function potential well is adjusted to fit the empirically determined binding energy (Lucovsky 1965). Other theories have been used to explain the deviation of the measured impurity binding energy from that calculated using the effective mass model. For example, see the Green’s function method of Chen and Sher which also applies to deep levels (Chen and Sher 1985). Glodeanu (1967) proposed a theoretical method that can be used to calculate the deep levels of impurities directly. He studied the bivalent substitutional impurities that can forms two localized levels in band gap. He adopted a helium-like model to approximate a single electronic energy band, and then calculated the deep donor and acceptor levels of many impurities in GaAs and Si. Chen and Sher have warned that

18

2 Impurities and Defects

the deep levels are quite sensitive to the quality of the underlying band structures of the host material, so this method can only be expected to produce approximate results (Chen and Sher 1985). For a donor with two valence electrons, the Hamiltonian operator can be written as follows: H D

„2 .r 2 C r22 / C V .r1 / C V .r2 / C Ueff .r1 ; r2 /; 2m 1

(2.27)

and the corresponding Schr¨odinger equation is: H ‰.r1 ; r2 / D E‰.r1 ; r2 /;

(2.28)

where V .r1 / is a periodic potential which denotes the interaction between one of the two electrons and the effective crystal field, similarly, V .r2 / is the periodic potential of the other electron. The last term in (2.27) is an approximation to the difference between the two electron Hamiltonian and its periodic part: Ueff .r1 ; r2 / D 

Ze e 2 Ze e 2 e2 :  C "r1 "r2 " jr1  r2 j

(2.29)

The first two terms in (2.29) denote the interaction between the two electrons and the screened positive charge Ze which is introduced to keep the crystal electrically neutral. The last term is the electron–electron interaction that gives rise to correlations and exchange. In (2.28), the wave function takes the form: ‰.r1 ; r2 / D

1 X c.k1 ; k2 /Uc;0 .r1 /Uc;0 .r2 /  exp.ik1  r1 / exp.i k2  r2 /; N k ;k 1

2

(2.30) where Uc;0 is a Bloch function evaluated at the location of conduction band minimum i.e., at k1 D 0. In general, Uc;0 satisfies the following equation:   „2 2   r1 C V .r1 / Uc;0 .r1 / D Ec;0 Uc;0 .r1 /; 2m

(2.31)

where is the volume of the primitive cell, and N is the number of primitive cells. If ‰ from (2.30) is substituted into (2.28), it reduces to a helium-like relation:   „2 Ze 2 Ze 2 e2   .r12 C r22 /  Fn .r1 ; r2 / D EFn .r1 ; r2 /:  C 2m "r1 "r2 " jr1  r2 j (2.32) Glodeanu (1967) determined the energy using variational calculus to solve (2.32). For Fn .r1 ; r2 /, a trial function with the following form was chosen: Fn .r1 ; r2 / D

  3 Z0 Z0 exp  .r C r / ; 1 2 r0  r03

with r0 D

„2 " : m e 2

(2.33)

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

19

Then two expressions for the ionization energy are obtained:   5 25 2 2 ; and E2 D aZeff  Zeff C ; E1 D a Zeff 4 128

(2.34)

where a is a parameter, a  m =", and Z 0 D Zeff 

5 : 16

(2.35)

For the impurities Cr, Cd, and Zn, the effective mass used is m D 0:34m0 , A is an acceptor, D is a donor. Because it is difficult to determine the differences among impurity atomic cores correctly, Zeff in (2.34) is regarded as an undetermined parameter chosen to minimize the quadratic sum of the relative error between the theoretical and the experimental results. Table 2.4 shows the predicted theoretical ionization energy and the experimental results in GaAs, Ge, and Si. The Zeff is also listed. The reference value of a donor level is the minimum of the conduction band, and the reference value of an acceptor level is the maximum of valence band. This is a relatively rough early method. It only provides an approximate estimate. Swarts et al. (1982) calculated the energy state of vacancies in HgCdTe using a Green function method. They used an empirical tight binding model truncated at second neighbors. Hass et al. (1983), in a paper published at nearly the same time, also used an ETB model truncated at second neighbors but they chose a different parameter set. Both added a spin-orbit Hamiltonian and used impurity potentials derived from the differences between atom term values of the impurity and the

Table 2.4 Ionization energies of deep levels of impurities in GaAs, Si, and Ge taken from theory and experiments E1 E2 Crystals GaAs Si

Ge

Impurities Cu S Ni Co Zn Se Te Mn Co Fe Ni Cr Cd Zn

Types A D A A A D D A A A A A A A

Zeff 2 2.145 2.380 2.515 2.428 2.275 2.195 2.475 2.815 3.060 2.753 2.580 2.735 2.050

Theoretical value 0.171 0.206 0.280 0.328 0.297 0.138 0.124 0.177 0.249 0.312 0.234 0.068 0.079 0.034

Experimental value 0.15 0.18 0.23 0.35 0.31 0.14 0.11 0.16 0.25 0.34 0.22 0.07 0.06 0.03

Theoretical value 0.407 0.447 0.550 0.614 0.573 0.285 0.262 0.322 0.431 0.509 0.413 0.123 0.138 0.078

Experimental value 0.47 0.52 0.70 0.58 0.55 0.28 0.30 0.37 0.43 0.47 0.44 0.12 0.20 0.09

20

2 Impurities and Defects

Fig. 2.1 The energy levels of vacancies as a function of the composition x, circular dots denote anion vacancies, and triangular dots denote cation vacancies

lattice atom for which it was substituted. They used the coherent potential approximation to get the host alloy band structures. The defect energies were calculated using a Green function method. The two calculations produced similar results. The Swarts calculation indicated that the Te vacancy has an energy level in the band gap, and one far above the conduction band edge. The energy level of a Hg or a Cd cation vacancy lies very close to valence band edge in an ideal crystal model. If a Coulomb interaction and lattice distortion corrections are taken into account, few energy levels lie in the band gap. Figure 2.1 shows the calculated energy levels of vacancies as a function of the composition x. This calculation does not predict the observed behavior. A likely cause of the error lies in the starting host band structures and the way the impurity potential is assigned. Unless they are close to correct the predicted defect levels will not be correct (Chen and Sher 1985). Kobayashi et al. (1982) also calculated the energy band structure of CdTe, HgTe, and Hg0:84 Cd0:16 Te with an empirical tight-binding approximation Hamiltonian truncated at first neighbors but with an extra s state added. They also used a Green function method. They have determined scaling relations for each of the tight binding parameters of the host lattice to generate their band structures, and provided rules for deciding on the defect potentials. Then, they calculated the energy levels of sp 3 bound defect states. In their calculations they have ignored the spin–orbit interaction, the long-range Coulomb interaction outside of the central primitive cell, the long-range part of the defect potential, and any lattice relaxation in the defects surroundings. So, the problem was simplified with the nondiagonal terms of matrix elements of defect potentials all set to zero. Also in the calculation no account is taken of the electron–electron interactions. When the spin is ignored, the group

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

21

point symmetry of the lattice is Td , and the energy levels of the bound states which take sp 3 as basis vectors are a onefold degenerate A1 energy level (S -like state) and a threefold degenerate T2 energy level (P –like state). If the spin is taken into account but the spin–orbit interaction is excluded, all the four of the above energy levels become twofold degenerate levels. Furthermore, if the spin–orbit interaction is taken into account, the above T2 energy level with sixfold degeneracy becomes a 7 energy level with twofold degeneracy (P1=2 -like state) and a 8 energy level with fourfold degeneracy (P3=2 -like state). On the other hand, the A1 energy level with twofold degeneracy is still twofold degenerate when the spin–orbit interaction is included, namely, it becomes a 6 energy level (S1=2 -like state) in the two-group expression. These symmetry considerations change the secular equation for the defect energy levels E to (Chen and Sher 1985): 1  v˛ g˛ .E/;

(2.36)

where ˛ designates the symmetry of a local state, e.g., 6 ; 7 ; and 8 on an atomic site of the zinc-blend structure, and g˛ .E/ is the diagonal matrix element of the host-crystal green function. g˛ .E/ can be calculated from the partial density of states (PDOS) by: Z ˛ ."/ g˛ .E/ D d": (2.37) .E  "/ The PDOS is given by: ˛ ."/ D

X

  jan˛ .k/j2 ı "  "n .k/ ;

(2.38)

nk

where "n .k/ are the band energies of the host crystal and an˛ .k/ are the probability amplitudes of the band states in the Bloch basis. The integrals in (2.37) over the Brillouin-zone must be done numerically. Solutions to (2.36) give the energy levels found by Kobayashi et al. for the substitutional impurities in HgCdTe, shown in Figs. 2.2 and 2.4. Figure 2.2 shows the deep levels of S1=2 -like states with 6 -symmetry as a function of the alloy composition x when impurity atoms occupy cation-sites. The two thick lines in Fig. 2.2 denote the energies of the conduction band minimum and the valence band maximum, respectively. The energy levels of S1=2 -like states for all the impurities that occupy cation-sites in CdTe are shown on the right vertical axis where many element symbols are labeled. The thin lines denote the energy levels of the impurities in the band gap of Hg1x Cdx Te.x < 1/. The trends with alloy composition x are shown only for selected impurities. The dashed curves indicate resonant levels in the conduction band or the valence band. Figure 2.3 shows P1=2 like state and P3=2 -like state deep levels as a function of the alloy composition x when substitutional impurities occupy cation-sites. Figure 2.4 shows P1=2 -like state and P3=2 -like state deep levels as a function of the alloy composition x when substitutional impurities occupy anion-sites (Te-site).

22

2 Impurities and Defects

Fig. 2.2 The 6 -symmetric (S1=2 -like state) deep levels of substitutional impurities on cation-sites as a function of the alloy composition x

Fig. 2.3 The 7 -symmetric (P1=2 -like state) and 8 -symmetric (P3=2 -like state) deep levels of substitutional impurities on cation-sites as a function of the alloy composition x

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

23

Fig. 2.4 The 7 -symmetric (P1=2 -like state) and 8 -symmetric (P3=2 -like state) substitutional impurity on anion-sites deep levels as a function of the alloy composition x

From these calculated results, we find that the deep levels have slopes dE=dx somewhat smaller than dEg =dx. Thus, a defect on a cation site with level at Eg =2 in CdTe would tend to remain near the center of the gap for a considerable range of alloy compositions. Anion site defects have dE=dx values that are very small, and so appear to be “attached” to the valence band. The results of Jones et al. (see in Sect. 2.1.5) suggested that, for 0:2 6 x 6 0:4, the deep levels at Eg =2 and 3Eg =4 may be due to a cation vacancy (presumably singly and doubly charged, respectively) (Jones et al. 1982). This identification is inconsistent with this work where the cation vacancies only exhibit levels in the gap that lie close to the valence band edge at higher concentrations. Because the conclusions deduced in the next paper to be discussed (Chen and Sher 1985), points out inaccuracies of the Swarts, Kobayashi, and Hass results, we will not elaborate further on the conclusions drawn form these papers. The sources of the errors are the choice of host band structures and the method of choosing the effective potentials to assign to the impurities. The Hamiltonians used by Swarts, Kobayashi, and Hass are all ETB with short range cut-offs. Swarts and Hass add a spin orbit Hamiltonian and Kobayashi an additional s-state to the normal sp3 hybrid basis. These Hamiltonians produce flawed band structures that have band states that are among other things too broad, and in some cases have secondary band gaps. The PDOS to which the impurity levels are

24

2 Impurities and Defects

sensitive are imperfect. To correct these defects, Chen and Sher (1985) employed their orthonormal orbital (ONO) band structures. Their method of generating the Hamiltonian consists of four steps. 1. It starts with four Gaussian orbitals per atom and empirical pseudopotentials (Chen 1977), and computes the Hamiltonian matrix H.k/ and the overlap S.k/ as was done by Kane (1976) and Chadi (1977). 2. The Gaussian orbitals are transformed into ONO’s, so H.k/ is transformed into H0 .k/ and S into the identity matrix. The band structures calculated from H0 .k/ are accurate to within 5% of those done by more sophisticated means using the same potentials. 3. A spin–orbit Hamiltonian in the ONO basis is incorporated. 4. To compensate for the effects of the truncated basis and the nonlocal potentials, a perturbation Hamiltonian H1 is added. H1 has the form of a truncated ETB Hamiltonian with parameters adjusted to fine tune the important band energies and effective masses (Chen and Sher 1980, 1981a, b). There are two major differences between this method and more traditional ETB methods. (1) This method includes all the long ranged interactions so the high Fourier components are present to properly reproduce sharp band curvature features. (2) Proper wave functions are produced so predictions of other quantities, like transport properties and lifetimes, are accurate. The second ingredient to the impurity deep state calculation are the potentials, ’ . These potentials are set by the difference between the term values derived from free atom atomic pseudopotentials of the impurity and the host atom that is replaced. The potentials used by the different authors depend on the particular pseudopotentials they used. However, none of them are completely trustworthy, because the effective pseudopotentials of the atoms in the crystal differ from those of the free atom. Because of this uncertainty Chen and Sher did the deep level calculations for a range of potentials around the free atom result. For CdTe they used potentials varying from 0:5 to 2.0 eV to test the sensitivity to these choices for different impurities. The results are collected in Figs. 2.5–2.8 and Table 2.5 for the four papers, (Chen and Sher 1985) labeled a, (Hass et al. 1983) labeled b, (Swarts et al. 1982) labeled c and (Kobayashi et al. 1982) labeled d. These figures are plots of E vs. v for the 6 , and 7 symmetry states for a variety of impurities substituted on the Cd and Te sublattices. The vertical lines identify the locations of the potentials v derived from the term value differences using the Chen and Sher assignments. It is evident that there are substantial differences among the deep state assignments from the four papers. Because the E vs. v curves depend sensitively on the partial densities of states, which differ greatly among the four approaches, these assignments also differ. To emphasize the impact of the choice of v on these differences a list of E values is given in Table 2.5 for v and v C 1 eV. The E values deduced from v C 1 eV are denoted rE. This paper emphasizes the uncertainties in the assignments of deep state energies in various approximations so it is a bit disingenuous to discuss results. To illustrate this point, consider the following examples: Table 2.5 has Li on a Te site with an

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects Fig. 2.5 The E vs. v curves for the 6 states on a Cd site

Fig. 2.6 The E vs. v curves for the 6 states on a Te site

Fig. 2.7 The E vs. v curves for the 7 states on a Cd site

25

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Fig. 2.8 The E vs. v curves for the 7 states on a Te site

Table 2.5 Defect energy levels E and changes rE due to a 1 eV change in the impurity potential parameter. All energies are in units of eV. V0 stands for an ideal vacancy Model a Model b Model c Model d Defect E E E E E E E E

6 on Cd site Ga 1.29 0.39 1.42 0.24 1.33 0.23 1.57 0.18 C 0:21 0.09 0.38 0.09 0.36 0.13 0.74 0.08 Si 0.67 0.30 1.02 0.10 0.93 0.19 1.27 0.15 P 0:19 0.11 0.39 0.09 0.38 0.08 0.75 0.08 O < 0:5 0:02 0.02 0.04 0.01 0.32 0.02 Te 0:13 0.13 0.44 0.10 0.42 0.08 0.79 0.09 Cl < 0:5 0.06 0.03 0.10 0.02 0.41 0.04 < 0:5 < 0:5 0:30 0:20 V0

7 on Cd site C 0:02 0.37 1.32 0.22 1.59 0.20 1.39 0.19 Si 1.57 0.65 >2:0 >2:0 >2:0 P 0.16 0.38 1.48 0.26 1.73 0.23 1.52 0.21 O < 0:5 0.89 0.14 1.22 0.13 1.03 0.12 Te 0.48 0.55 1.60 0.29 1.88 0.23 1.66 0.24 Cl < 0:5 0.96 0.17 1.29 0.14 1.09 0.14 V0 < 0:5 0.00 0.21 0.06

6 on Te site Li 0.14 0.29 1.28 0.22 1.15 0.35 0.76 0.25 Cu < 0:5 0.54 0.42 0.12 0.52 0.03 0.32

7 on Te site Ag 1.89 0.32 1.26 0.22 1.21 0.23 0.99 0.20 Cd 1.66 0.34 1.11 0.26 1.05 0.26 0.85 0.22 Ga 0.98 0.49 0.61 0.33 0.55 0.32 0.40 0.30 Si 0:07 0.40 0:11 0.36 0:13 0.38 0:38 0.72 Sn 0.28 0.47 0.15 0.31 0.13 0.24 0.02 0.28

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27

s level of 0.14 eV in Model a, so one may be tempted to relate it to the acceptor state identified experimentally (Zanio 1978). However, this is not the hydrogenic acceptor stare on a Cd site that one might expect. One might also want to assign the 1=3 and 2=3 gap states for the Te antisite p levels on the Cd site found from Model a as those seen in experiments (Jones et al. 1982; Collins and McGill 1983). Because of the large uncertainties in the calculation, these results should be regarded as suspicious surprises rather than confirmations.

2.1.4 Doping Behavior Berding et al. (1997, 1998c), Berding and Sher (1998a) were well aware of the uncertainties in the deep state predictions of the earlier work. They set out to eliminate the approximations responsible for these uncertainties and to advance the work from the one that focused on the 0 K predictions to one that could deal with finite temperatures and thus with realistic situations. In addition of their excellent band structures, they calculated energies for impurities that are situated on relaxed sites. Berding et al. (1997) have discussed the behavior of the elements of group IB and IVA in periodic table as acceptor impurities in HgCdTe. By means of the full-potential linearized muffin-tin orbital method (FP-LMTO method), they have calculated approximately the electron total energy and localized energy level in the band gap, and have calculated the temperature dependence of the concentration of impurities and grown-in defects. Details of these theoretical calculations can be found in the articles of Sher’s group, for reference (See Berding et al. 1998c; Berding and Sher 1998a). The calculated results indicate that Cu, Ag, and Au occupy the cation vacancy and are p-type dopants. The calculated results of Berding are shown in Fig. 2.9, which gives the acceptor concentrations for a 1017 cm3 doping level of group I impurities occupy Hg sites in HgCdTe at 500ı C as a function of the Hg partial pressure. 500ı C is near to a LPE growth temperature. Figure 2.9 also shows the concentration of VHg as a function of Hg partial pressure in the range between 0.1 and 10 atm. The densities of Cu, Ag, Au, and Te occupying Hg sites, and, Cu or Ag occupying interstitial positions are also presented. When 1017 cm3 , Cu is present 1013 cm3 occupy interstitial positions, and for Ag and Au, the interstitial densities are smaller and are 1011 and 1010 cm3 , respectively. The LPE growth temperature of HgCdTe is about 500ı C. Following growth by LPE, materials are often subjected to a low-temperature (200–250ı C) anneal under Hg saturated conditions to remove the as-grown Hg vacancies. For material equilibrated under these conditions, 100% activation as acceptors is found for Cu, Ag, and Au, with the densities of interstitial atoms being less than 1010 cm3 for all three. However, it is impossible to prolong the annealing times infinitely so the slower diffusing species may not reach their equilibrium.

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Fig. 2.9 Acceptor concentrations as a function of Hg partial pressure in HgCdTe at 500ı C, near to typical liquid phase epitaxy (LPE) growth temperatures, when the elemental group I impurities occupy Hg vacancies

Figure 2.10 shows the results of concentration of the group V elements P, As, and Sb, including as a function of the Hg partial pressure when they are substituted on the anion and cation sublattices. From Fig. 2.10, we see that except at very high Hg partial pressures the concentration of AsHg is greater than that of AsTe , indicating that As substitutes on Hg sites where it is a donor, more easily than on Te sites where it is an acceptor. Sb behaves the same as As. Only when Hg partial pressure approaches to 10 atm or more, does the concentration of AsTe and SbTe become greater than that of AsHg and SbHg . But for P doping, the concentration of PTe is greater than that of PHg when the Hg partial pressure reaches only 1 atm. The group V dopants are exhibit compensation at lower Hg partial pressures. After annealing at a temperature of 240ı C, the concentrations of P, As, and Sb occupying the anion sublattice do increase, while those occupying the cation sublattice decrease, but there is still quite a large concentration range were the materials are compensated semiconductors, as shown in Fig. 2.11. From above analysis, we see that, for the group V dopants in HgCdTe with LPE growth on the Hg-rich side of the existence region, then the elements P, As, and Sb

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29

Fig. 2.10 Defect concentrations as a function of the Hg partial pressure in HgCdTe equilibrated at 500ı C, near the LPE growth temperature, when some Te and Hg sites are occupied by P, As, and Sb respectively

will occupy the Te sublattice and be acceptors. Then elements of P, As, and Sb will occupy the Hg sublattice to become donors if the material is grown from Hg-rich solutions. They are some what compensated at the extremes of the partial pressure regimes. In order to get p-type dopants, it is best to grow HgCdTe by LPE from a Te-rich solution and then anneal the samples at a temperature of 240ı C. Besides, when the materials are annealed for a long time at the temperature of 240ı C, the self-compensation behavior can be eliminated effectively. In the following, we will discuss As-doped HgCdTe grown by MBE. The growth temperature is about 180ı C when HgCdTe is grown by MBE. Berding et al. developed a similar theoretical calculation for MBE growth (Berding et al. 1998c; Berding and Sher 1999a, b), and discussed the amphoteric behavior of impurity As in HgCdTe. The detail of theoretical calculation is found in Berding et al. (1998c) and Berding and Sher (1998a). Though MBE growth is not an equilibrium process, it can be regarded as equilibrium growth approximately, so the defect distribution is near-equilibrium. The optimal temperature for MBE growth is 185–190ı C, but can be slightly lowered to 175ı C to incorporate the As into the HgCdTe more effectively.

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Fig. 2.11 P, As and Sb defect concentrations on the anion and cation sublattice sites as a function of Hg partial pressure for HgCdTe samples equilibrated at 240ı C. The Hg vacancy and Te antisite concentrations are also shown

Under the condition of Te saturated, that is to say, PHg D 105 atm, much less than 1% of the As will be incorporated on the Te sublattice. On the contrary, almost all the As occupy the Hg sublattice, and as shown in Fig. 2.12, 30–50% of the AsHg forms a neutral complex bound to VHg . From Fig. 2.12 we can see that the concentration of AsHg –VHg is only slightly less than that of AsHg . The remaining AsHg are donor impurities. Therefore, when the concentration of As is relatively low, the materials are p-type semiconductors because of the VHg acceptors, then as the concentration of As increases it becomes n-type with some compensating VHg acceptors. Specifying the Cd concentration to be x D 0:3 and the total As concentration to be 1016 cm3 , in their calculations Berding et al. presented the defect concentrations as a function of Hg partial pressure at the annealing temperature of 220ı C shown in Fig. 2.13. From Fig. 2.13, we see that under a Hg saturated condition at a Hg partial pressure is 0.1 atm almost 99% of As impurities occupy Te sites and therefore are acceptors. Arsenic almost entirely occupies Hg sites when the sample is grown at 175ı C by MBE, and can transfer to Te sublattice sites through a sequence of annealing steps ranging from 350 to 220ı C.

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31

Fig. 2.12 Defect concentrations in HgCdTe as a function of the As concentration at 175ı C in samples grown by molecular beam epitaxy (MBE) under Te saturated conditions

Fig. 2.13 Defect concentrations with As-doped HgCdTe as a function of the Hg partial pressure at an annealing temperature of 220ı C for a sample grown by MBE under Te saturated conditions

Berding et al. (1998c) have proposed a model for the arsenic transfer from the cation to the anion sublattice. According to this model, in as-grown materials the As atoms occupy cation sites and some of these AsHg atoms are bound to Hg vacancies in the initial state to form neutral complexes, AsHg –VHg . This AsHg –VHg defect complex will be present at high density in the as-grown material. The first step of the p-type activation process is, Te ! VHg D TeHg C VTe , i.e., a Te atom transfers from a Te lattice site into a cation vacancy site, creating a Te antisite, TeHg . The second step permits, the VTe to interact with the AsHg –VHg complex and the AsHg transfers into the vacated Te site, forming a AsTe leaving behind a Hg vacancy, or .VHg  AsHg / C .VTe  TeHg / D AsTe C .VHg  TeHg /. In the final step, the VHg vacancy and TeHg antisite form a bound neutral pair (Berding et al. 1995), which diffuses to the surface where in picks up a Hg atom from the high partial pressure Hg atmosphere to become a new HgTe molecule or the TeHg evaporates. Figure 2.14 shows the schematic process of the As atom transfer in the proposed model.

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Fig. 2.14 Schematic of the arsenic transfer process from the Hg to the Te sublattice in the proposed model

Fig. 2.15 Defect concentrations as a function of temperature and Hg partial pressure in a possible annealing process for Hg0:7 Cd0:3 Te

The above model describes the process through which an As atom transfers onto Te site after annealing when it initially occupied a Hg site in the as-grown material. Following this model, one can calculate the concentration of different kinds of defects under different annealing condition, and can give advice about a proper annealing process. Figures 2.15 and 2.16 show the calculated results. In Fig. 2.15, the material starts from the MBE growth condition at 175ı C, is heated to 220ı C under Te-saturated conditions, and is then subjected to increasing Hg partial pressures from 106 to 101 atm while the temperature is held at 220ı C. It can be seen

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

33

Fig. 2.16 Defect concentrations as a function of temperature and Hg partial pressure in a higher temperature annealing process for Hg0:7 Cd0:3 Te

that the AsTe population sharply increases and the concentrations of the AsHg , and the AsHg –VHg complex sharply decrease. In Fig. 2.16, starting from MBE growth conditions at 175ı C, the material is heated to 350ı C under a Te-saturated condition, and is then subjected to increasing Hg partial pressures from 103 to 1 atm while the temperature is held at 350ı C; then the temperature is reduced to 220ı C under a Hg-saturated condition. Then the AsTe population rises to 1018 cm3 , the AsHg population goes to 1016 cm3 , and the concentration of the VHg and the AsHg –VHg complex decrease to below 1011 cm3 . For both of the paths in Figs. 2.15 and 2.16, the AsHg population sharply decreases and the AsTe population sharply increases. In the second process there is more thermal energy to surmount the activation barrier to the transfer of the As atom from the Hg to the Te sublattice. At the same time, there are sufficient vacancies present to promote the reactions in the annealing process. In addition, in both processes one needs to traverse the phase field from Teto Hg-saturated conditions slowly enough to allow enough time for the As transfer to occur before the Hg vacancies are depleted. The above model has also been used to discuss HgCdTe with Li, Na, and Cu doping by LPE growth. Berding et al. (1998b) have discussed the Hg1x Cdx Te, x D 0:22, by LPE growth, and calculated the Li, Na, and Cu defect density as a function of the Hg partial pressure. They also treated these element’s behavior in CdTe substrates. It was found that all three impurities are preferentially incorporate on the cation sublattice, where they are acceptors. Then keeping the Hg partial pressure fixed, and reducing the temperature, the concentration of Li, Na, and Cu interstitial atoms increases, while the concentration of substitutional impurities decreases. Under Hg-saturated low temperature annealing conditions, Li and Na diffuse out of the CdTe substrate toward a HgCdTe layer because of a free energy difference. Thereby, CdTe and CdZnTe substrates can be preannealed to reduce the group I impurities greatly. Then the sacrificial HgCdTe layer is etched off leaving a purified substrate behind. This substrate is then used to grow a group I element free HgCdTe epitaxial layer by LPE. Details of the calculated results can be found in Berding et al. (1998b).

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2.1.5 Experimental Methods 2.1.5.1

High-Frequency and Low-Frequency Capacitance Measurement Principles

For a planar device semiconductor, generally speaking, a passivation layer or a dielectric layer, as a protective film on its surface, is needed to promote the operation of this class of devices. However, interface defect states are inevitably introduced. These defect states will become carrier scattering centers, and will reduce the mobility and lifetime of carriers and the signal-to-noise ratio (SNR) of devices. Therefore, it is necessary to detect and control these defect states, and the usual method is a combination of high- and low-frequency capacitance measurements. The procedure starts by photoengraving a metallic gate electrode on the insulating layer placed on the surface of a semiconductor, to make a MIS structure. Then measure the high- and low-frequency capacitance of this structure. From these measurements the distribution of interface defect states in the band gap can be deduced. Usually the interface state energies are distributed continuously throughout band gap in what is referred to a U-shaped distribution with its minimum near mid-gap, and the filled electron interface state populations determined by the Fermi level. As the surface potential of a semiconductor changes, the Fermi level at the interface will change accordingly. Then the number of electrons filling the interface states will change, resulting in an electron exchange between interface states and the bulk semiconductor. When a direct current bias and alternating-current small-signal are applied, the interface will charge and discharge as the surface potential changes. The interface states produce a response to the changing surface potential equivalent to a capacitance, Css , called the interface-state capacitance. When the surface potential change is d's , the interface charge concentration will change by an amount dQss . So we have: (2.39) Css D dQss =d's : For an MIS structure, the measured capacitance Cm is the series combination capacitance of its insulating layer capacitance Ci and the total interface capacitance, Cit ; .Cm /1 D .Ci /1 C .Cit /1 :

(2.40)

Since the time constant for the exchange of electrons between interface states and the bulk is relatively long, the change of the interface state charge can keep up with the variation of an alternating-current small signal only when the frequency of alternating-current small signal is very low so it can contribute to the capacitance. Then the measured capacitance Cm is just CLF , and Cit consists of surface depletion/accumulation layer capacitance, Cs and an interface state capacitance, Css . When the alternating-current small signal frequency is very high, the interface state charge can not keep up with the variation rate to exchange electrons with the bulk, so does not contribute to the capacitance. Consequently, the measured capacitance

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35

Cm is just CHF , and Cit is only the semiconductor surface capacitance Cs , so we can get: .CLF /1 D .Ci /1 C .Cs C Css /1 ; .CHF /1 D .Ci /1 C .Cs /1 :

(2.41) (2.42)

Eliminating, Cs from (2.41) to (2.42), yields an expression for the interface state capacitance: Css D Ci  Œ.Ci =CLF  1/1  .Ci =CHF  1/1 :

(2.43)

Again from (2.39), the interface state density as a function of the surface potential can be found: (2.44) Nss D Css =e Therefore, the interface state density can be obtained from the high- and lowfrequency capacitance spectra and (2.43) and (2.44). The energy level locations of the interface states in the band gap can be obtained from an energy band potential model of a two-dimensional electron gas and the low-frequency capacitance spectra (Nicollian and Brews 1982). As examples, now we will introduce the measured results of the density of states of a ZnS/MCT, and an SiO=SiO2 /InSb interface. MCT and InSb are made into MIS structures, and their high- and low-frequency capacitance spectra are measured (shown in Figs. 2.17 and 2.18). The distribution of interface states was calculated using the method mentioned above, and shown in Figs. 2.19 and 2.20. The parameters of the samples, and the test condition are as follows: (1) an n-type Hg1x Cdx Te, x D 0:30, donor concentration ND  1:7  1014 cm3 , an insulator layer thickness of the ZnS is 200 nm, the area of metallic gate electrode is 0:002 cm2 , the testing temperature is 80 K, and the testing frequencies are 20 Hz and 10 MHz respectively;

Fig. 2.17 The high- and low-frequency capacitance–voltage (C –V ) spectra of a mercury cadmium tellurium (MCT) (x D 0:30) metal–insulator–semiconductor (MIS) device

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Fig. 2.18 The high- and low-frequency capacitance–voltage (C –V ) spectra of an InSb MIS device

Fig. 2.19 The distribution of interface states in an MCT MIS device

Fig. 2.20 The distribution of interface states in an InSb MIS device

(2) an n-type InSb, donor concentration ND  2:0  1014 cm3 , insulator layer thickness of SiO=SiO2 is about 180 nm, the area of the metallic gate electrode is 0:00785 cm2 , the testing temperature is 80 K, and the testing frequencies are 300 Hz and 104 kHz, respectively.

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37

From Figs. 2.19 to 2.20, we can see that the distributions of interface state densities for the two kinds interfaces exhibit the usual “U” shape, the minimum of the interface state density (located at about the middle of band gap) is of the order of 1011 cm2 . Further experiments and calculations indicate that there is a fixed positive charge with a density 8:2  1011 cm2 and a slow hole trap density of 4:6  1010 cm2 in the ZnS dielectric layer. There is also a fixed positive charge density of 1:0  1012 cm2 , and a slow hole trap density of 2:4  1012 cm2 in the SiO=SiO2 dielectric layer.

2.1.5.2

Deep Level Transient Spectroscopy

Deep level transient spectroscopy (DLTS) is an important method to determine deep level energies and their response properties in semiconductors. This method measures the temperature dependence of the admittance spectrum, or the temperature dependence of the capacitance spectrum. At a given temperature, if a deep level releases (or capture) carriers, the admittance will change. The principle is the same as a measurement of the capacitance. A scanning DLTS spectrum at different temperatures can separately detect all kinds of deep levels depending on their energy distributions in the band gap (each has a different DLTS peak). From the DLTS peak locations and peak heights, one can obtain important parameters, such as the energies of the deep levels, carrier densities, and the cross sections of the trapped carriers. Detailed experimental methods and results are presented in Sect. 2.3.

2.1.5.3

Photoluminescence Spectroscopy

Photoluminescence (PL) spectroscopy is a measurement tool, that can be used not only to deduce the conduction and valence band shapes and the exciton electronic states in semiconductors, but also the energy shapes of the impurity defect states. In a sense, the PL process is the inverse of the light absorption process. It can be divided into three subprocess: 1. An external exciting light (or an external injection current, or irradiation beam) excites carriers in the material, forming a nonequilibrium electron–hole pair distribution. 2. The nonequilibrium electron–hole pair reaches a relatively low energy state in a radiative or a nonradiative recombination process. 3. The light generated by a radiative recombination process propagates within the semiconductors. Since any light emitted in the radiative recombination process will be reabsorbed again during propagation (radiation trapping), photoluminescence can occur only from the range of several electron diffusion lengths of the irradiated surface of a semiconductor.

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Therefore, a PL experiment has certain limitations on the experimental technique and material structures to which it can be applied. For relatively thick samples, the PL detector should be placed above the irradiated surface of the semiconductor; and for relatively thin samples, the PL detector can be placed at the back of the irradiated surface. Furthermore, the surface perfection of the material is important because all kinds of defect states, such as surface states and dislocations which may induce nonradiative recombination, should be minimized. Otherwise, a PL experiment is insensitive. The dynamics of the PL process can be judged by the measured peak position of the spectrum and the curves’ shapes compared to those of a theoretical analysis. Thereby, the impurity state density in a material can be deduced. Using a PL spectrum to investigate impurities in HgCdTe materials encounters a new difficulty, which is mainly due to the HgCdTe material properties. The band gap width of HgCdTe is relatively small, and the ionization energy of donors is only 0:04 eV, hardly binding electrons and leading to the materials being in a completely ionization state even at relatively low-temperatures. The PL spectrum basically is in the wave length range of the mid- to far-infrared. In this range, the responsivity of detectors is relatively low, and the background radiation is rather strong. Furthermore, nonradiative recombination in HgCdTe is relatively fast, so a PL signal is also small. All these factors degrade the detection efficiency of the PL spectra, and the difficulty is bad especially for low alloy compositions. So, there are few research reports about the PL of MCT, and they mainly concentrate on higher alloy composition HgCdTe materials. To investigate small alloy compositions with PL, employment of far infrared bands is necessary. This topic will be discussed again in another section.

2.1.5.4

Photothermal Ionization Spectrum Principles

Since Lifshits et al. discovered the photothermal ionization phenomenon with a semiconductor infrared-photoconductivity experiment in the 1980s, photothermal ionization spectroscopy (PTIS) has been used widely to investigate the shallow impurity behavior in semiconductors, especially for impurities in high-purity semiconductors. At low-temperature, impurity ionization can be divided into two steps: 1. The ground state of the impurity is excited by a photon to an excited state. 2. Then it ionizes into the conduction band to provide conductance (shown in Fig. 2.21). Thus the photothermal ionization process combines the high-resolution of optics with the high sensitivity of electricity, to provide a useful means to observe micro-impurities in high-purity semiconductors. Obviously, PTIS has rigorous requirements for experimental conditions. First, the temperature cannot be too high to enable the impurity to stay in its ground state; second, the temperature also cannot be too low so there are enough phonons to help the impurities ionize from the excited state into the conduction band. Furthermore, good ohmic contact electrodes are required. It is difficult to investigate the shallow impurities in narrow-band

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39

Fig. 2.21 A sketch of photothermal ionization process

gap semiconductors InSb and MCT using this method, because it is difficult to fabricate sufficiently high-purity material. Furthermore, there are always distinct band tails in these materials, so shallow impurity energy levels are slightly removed from the band-edge. Under these conditions, localization can occur only at very lowtemperatures or by the application of very strong magnetic fields. Consequently, it is hard to satisfy these rigorous experimental conditions. So this method is usually only used to observe shallow impurities in high-purity GaAs, Si, and Ge.

2.1.5.5

Quantum Capacitance Spectrum Technology

The several of the experimental methods mentioned earlier can be used to investigate impurity defects with energy levels located in the band gap, but cannot test for resonant defect states. In narrow gap semiconductor materials, many “deep” levels caused by short-range interactions are located in the conduction band. These “deep” levels interact with the continuum states in the conduction band, forming resonant defect states. Generally speaking, it is comparatively troublesome to investigate resonant defect states, since it is hard to separate the resonant states from continuum conduction band states. There have been many theoretical and experimental efforts devoted to these aspects of the problem, such as the chemical trends theory of sp3 binding of deep trap levels, the measurement of transport under pressure, far infrared spectroscopy, etc. Here a new model for investigating resonant impurity defect states will be established based on the capacitance characteristics of narrow gap semiconductors. Band bending on the surface of semiconductors can be investigated with a capacitance–voltage (CV) measurement on MIS structures. For narrow band semiconductor MIS devices, quantization phenomenon can be found within the surface inversion layer. A ground state sub-band quantization level is located at a position E0 , which lies above conduction band minimum (shown in Fig. 2.22). When the magnitude of band bending is equal to Eg , that is when the conduction band minimum bends below the Fermi level, the inversion layer channel still cannot be filled by electrons. To the contrary, only when the energy band bending reaches Eg C E0 , i.e., when the ground state of the quantized sub-band lies below the Fermi level, can

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Fig. 2.22 An energy band bending sketch for a narrow band gap semiconductor MIS structure with resonant defect states

the inversion layer channel hold electrons. Therefore, the threshold voltage for the inversion layer formation is retarded. If there is a resonant defect state between the conduction band minimum and E0 , at ER as shown if Fig. 2.22, it will be reflected in the capacitance CV spectrum. If starting from the case of a flat band, with an impurity state lying far above the Fermi level so that it cannot bind electrons, then when the impurity state falls below the Fermi level because of energy band bending, electrons will fill the resonant defect energy levels. If the states’ density is high enough, this kind of electron filling will influence the charging and discharging process of the inversion layer and hence contribute to the capacitance. So, an extra peak will occur in the capacitance spectra before the MIS structure inverts. Some relevant information about the resonant defect state, such as its concentration, and the location of its energy level, can be obtained from its peak position and peak amplitude. When a resonant defect state is located at above E0 and is an acceptor-type (see ER ’ in Fig. 2.22), then ER ’ also can be observed from a capacitance spectrum. Since the trapping and release times of electrons from impurity defect states is usually longer than that for continuum states, when an MIS device is inverted, the acceptortype resonant defect states will repel other electrons occupying continuum states after it captures electrons, leading to a decrease of the number of electrons that contribute to the capacitance. So, the rate of the capacitance increase slows, or even decreases. With an increase of test frequency, the probability of resonant defect states capturing electrons becomes smaller, and their influence on the capacitance also gradually weakens. Thus information about resonant defect states, their concentrations, the location of their energy levels, and the lifetime of trapped electrons, can be obtained from this frequency-conversion capacitance spectroscopy (FCS) measurement.

2.1.5.6

Positron Annihilation Spectra for MCT

Positron annihilation spectra technology (PAT) was established based on the microscopic distribution of positrons in solids being related to the interaction between a positron and an ion core, as well as an electron. Since the thermal momentum of a positron is almost zero, and a positron is a particle with a light mass and a positive charge, it will suffer a strong repulsive interaction with an ion core. Therefore,

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41

when positrons are in a perfect crystal, they are located mainly in interstitial sites and can diffuse freely. Under this condition, positrons are free particles. When a positron is in an imperfect crystal with a lattice vacancy, or in the vicinity of a dislocation core, these defects will strongly attract the positrons since these vacancy-type defects lack ion cores and electron redistributions will induce a negative potential at such sites. So, positrons will tend to be in bound states around these sites. All the positrons, whether they are in free or bound states, will be annihilated with electrons. The densities of valence electrons in such defect sites is lower than that of lattice atoms in a perfect crystal, so the probability of positron annihilation at defect sites will be reduced, thereby leading prolonged lifetimes. The lifetime of positrons in a perfect crystal lattice, is shorter. Thus the defects in crystal can be detected quite sensitively with positron lifetime measurements. The measurement proceeds as follows. A positron source 22 Na releases a positron and at the same time, radiates a  photon with energy of 1.28 MeV. This photon sets the zero of time. The positron later annihilates with an electron in the sample after a time t releasing two  photons each with energy of about 0.511 MeV. Measuring the interval t between the 1.28 and a 0.511 MeV  photon, determines the lifetime of the positron in the sample. This kind of technology has been widely used for the past 20 years to study thermodynamics problems of hole-type defects in metals. In recent years, the technology has been used to investigate defects in semiconductors, but was seldom used to investigate defects in MCT. As an example, we will introduce measurement results of a positron annihilation spectrum for a highly doped p-type MCT sample. Choose a p-type MCT (x D 0:5) bulk material with a concentration of NAD D 1:5  1018 cm3 , then do an anodic sulfurisation on its surface, cut the sample into two pieces, fix them in a sample holder of the measurement system, and positron an 22 NaCl source on a site between two samples. The measurement system is a fast capture positron annihilation lifetime apparatus made by the ORFEC company with a resolution of 24 ps. The PAT spectrum of the sample is measured at room temperature. Every measurement lasts 8 h, and records about 2  106 positron annihilation events to build a spectrum. The system is scaled to a pair of single crystal Si wafers, and the measurement results are fitted by universal Positronfit software. Figure 2.23a shows the PAT spectrum of the sample mentioned above at roomtemperature. Figure 2.23b shows the measured PAT spectrum of the same sample at room-temperature after being stored at atmospheric pressure for 3-months. The fits to the two spectral lines are shown in Table 2.6. From Table 2.6, we find that there are three positron annihilation lifetimes observed in the sample. They are 1 D 237  288˙14 ps, 2 D 366  400˙22 ps, and

3 D 1;996  2;099 ˙ 43 ps. Generally speaking, the number of measured lifetimes reflects the number of possible defect species in the sample. Thus, we conclude there are three kinds of trapping mechanisms in the measured sample. The results of the second measurement following the 3-month interval are close to the original values lying within the statistical error. This result may be caused by the anodic sulfide stabilization, since an anodic sulfide can serve as a good CdS protective film on the surface of MCT. It will especially enhance the stability of p-type MCT

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Fig. 2.23 The positron annihilation spectra technology (PAT) spectrum of a p-type HgCdTe sample (a) and that for the same sample three months later (b)

Table 2.6 The results obtained by fitting to the positron annihilation spectra technology (PAT) spectrum at room-temperature

Lifetime of positron in ps and the relative intensity of the apparent spectrum

1 I1

2 I2

3 I3

The first measurement 237 ˙ 14 42:75 ˙ 10:39 366 ˙ 16 52:82 ˙ 10:31 1;996 ˙ 37 4:43 ˙ 0:12

Three months later 253 ˙ 10 59:02 ˙ 8:92 400 ˙ 22 37:9 ˙ 8:83 2;099 ˙ 43 4:07 ˙ 0:12

materials. Gely et al. (1990) have measured the PAT spectra of p-type MCT with different doping concentrations, and found that the positron lifetime remains almost unchanged and is about 309 ˙ 1 ps almost independent of temperature, when NAD > 1:709  1016 cm3 . Gely concluded that the lowest value of a positron lifetime is about 270 ˙ 10 ps in a perfect MCT crystal, which is very different from the example mentioned above. With high p-type doping the measured positron lifetime

2.1 Conductivity and Ionization Energies of Impurities and Native Point Defects

43

1 is shorter than 270 ps. Evidently, 1 results from a near perfect CdS protective film and on an MCT crystal. But because the thin CdS protective film thickness is 1 m, and the positron penetration depth is 0:3 mm, 1 results from a substantial thickness of perfect crystal. Thus the new positron lifetime for a perfect crystal is shorter than that of prior measurements, and we conclude that the earlier measurements were made on slightly imperfect crystals. Second, the measured 2 is about 30% larger than Gely’s value of 309 ps, a lifetime ascribed to Hg2C vacancies. The measured 3 is very large, and results from positron annihilation on the surface of the sample. This lifetime value and its intensity suggest this conclusion. There are theoretical calculations indicating that positron annihilation on a surface produces the longest lifetimes. Furthermore, the thickness of the surface layer is very small so positron annihilation on the surface, would lead to the observed very weak intensity.

2.1.5.7

Optical Hall Effect Measurements

For a p-HgCdTe sample with a concentration in the low range, NA 6 5  1015 cm3 , due to mixed conduction effects, one cannot deduce the acceptor concentration and energy level from the usual temperature dependent Hall coefficient. At the same time, in this range of acceptor concentrations the compensation from the residual donor becomes important. Bartoli et al. (1986) introduced an optical Hall measurement technology. They obtained acceptor concentrations, acceptor ionization energies, and the compensation degree using results from fits to the measured optical excitations at low-temperature. The light source used in these experiments is a variable temperature black body source when the implanted carrier concentration is low, otherwise it is a 50 W continuous CO2 laser light emitter when the implanted carrier concentration is high. A chopped light device is used to yield a flat 25 ms pulse. The optically excited carrier concentration found by a Hall coefficient measurement is nm D 1=eR.B D 500 G/. The m  nm curve can be obtained from the mobility m D m =nm e. m is the measured conductivity. The mobility of electrons is limited by the concentration of charged scattering centers: Ncc  NA C NDC C p:

(2.45)

At high-temperatures, the acceptors are all ionized and the hole concentration in the valence band is p D NA  NDC , then we have Ncc  2NA . While at lowtemperatures, the holes are frozen out, and p D 0, NA D NDC , so we have Ncc  2NDC (see Fig. 2.24). Therefore, the mobility is very sensitive to impurity compensation at low-temperature. Setting x D 0:225 and for a sample thickness of 50 m, Fig. 2.25 shows a theoretically calculated curve of the electron mobility as a function of the optically excited electron concentration for various donor concentrations ND . It can be seen from Fig. 2.25 that the electron mobility as a function of the optically excited electron concentration is very sensitive to the donor concentration. Therefore, the level of compensation ND can be obtained using ND as a parameter to fit the   n curve.

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Fig. 2.24 A sketch of the charged scattering center concentrations. (a) depletion at high-temperature (kB T >> EA ; Ncc D 2NA /; (b) hole frozen out at low-temperature .kB T << EA ; Ncc D 2ND /

Fig. 2.25 The electron mobility as a function of the optically excited electron concentration and the donor concentration

Figure 2.26 shows experimental dots for m  nm , and a theoretically fitted curve at a temperature of 11 K. ND is the only adjustable parameter when the fitting is executed, and the result obtained is ND D 3:9  1015 cm3 . After ND is determined, the hole concentration and the donor ionization energy can be calculated from the magnetic field dependence of the Hall data from the following formula: p.p C ND / 1 D NV exp.EA =kB T /; NA  p  N D 2

(2.46)

where ND is already obtained, and NA and EA are fitting parameters. Using a fit to the calculated p  T 1 curve, the measured the values of NA and EA can be extracted. Both the measured and the fitted curves are shown in Fig. 2.27. The values of fitting parameters are NA D 6  1015 cm3 and EA D 11 meV. The fitted result indicates that a single acceptor, most likely Cu, is the impurity in the sample. To fit the experimental p  T 1 obtained from the magnetic field dependence of the Hall coefficient, if the optimal agreement cannot be obtained using a single acceptor model,

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45

Fig. 2.26 The measured mobility (experimental dots) and a theoretically fitted curve at a temperature of 11 K

Fig. 2.27 The hole concentration as a function of the reciprocal temperature; the dots are the experimental data, and the curve is a fitted result

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2 Impurities and Defects

one can attempt to fit the experimental result using a double acceptor. So a distinction between single and double acceptor models can be deduced from the fitted results. Thus the optical Hall measurement is an effective method to observe the compensation degree, the acceptor concentration, and the acceptor ionization energy in a p-type HgCdTe.

2.2 Shallow Impurities 2.2.1 Introduction Figure 2.28 illustrates the relative energy level positions of impurity defects in HgCdTe. The ionization energy is about 16 meV for the shallow acceptor level associated with the Hg vacancy, and its concentration depends on the density of the vacancies. The measured ionization energy of the shallow acceptor level associated with group V substitutional impurities on Te sites differs slightly from that of the Hg vacancy. There are energy levels that resonate with conduction band above and near to the conduction band edge, which are the combination of Hg vacancies, VHg , with various impurity atoms or Te vacancies. In the band gap, deep levels are experimentally found in the energy positions 3=4Eg , 2=4Eg , and 1=4Eg above the top of valence band. The origins of these deep states will be discussed presently. Meanwhile, there are also other native point defects; Cd vacancies, and Hg, Cd, and Te interstitials, and antisite defects, as well as their compounds with other native point defects and impurities. To identify the impact of these levels, theoretical studies have been performed with first principals, tight-binding, and Green function methods. Experimental research has been carried out with various techniques, such as CV spectroscopy, high-pressure transport, DLTS, optical capacitance spectroscopy, far infrared spectroscopy, impurity cyclotron resonance (ICR), and far infrared photoconductivity as well as conventional transport methods.

Fig. 2.28 Relative energy level positions of impurity defects in HgCdTe

2.2 Shallow Impurities

47

As was shown in Sect. 2.5.4 of Vol. I (Berding et al. 1993, 1994), the combination of native point defects and impurities determine the electrical characteristics of HgCdTe alloys. In this study first principal’s codes were used to determine the formation energies and densities of various native point defects and defect complexes in HgTe within the existence region as functions of the Hg partial pressure at three important temperatures, 500, 185, and 220ı C. The 500ı C temperature is typical of LPE growth, the 185ı C is that of MBE growth, and 220ı C is typical of a Hg saturated annealing temperature following MBE growth. The highest densities are for VHg vacancies, TeHg antisites, and a complex of the two VHg TeHg . Te vacancies, VTe , while they have lower concentrations, also have important consequences on defect migration. The VHg is a shallow acceptor [possibly a double acceptor (Vydyanath et al. 1981)], and its density dominates over most of the Hg partial pressure range. However, at low Hg partial pressures where the VTe density approaches that of the VHg , the VHg TeHg complex density produces a state that resonates in the conduction band, and may exceed the VHg density to cause the material to become n-type as observed under these conditions. This conversion is most apparent at the lower temperatures corresponding to MBE growth and Hg saturated annealing conditions. For low impurity concentration material, at high Hg partial pressures the material is observed to convert once again from n- to p-type. The donors responsible for this conversion, called the “residual donors,” are unknown. They are present in highly purified material, and never have been successfully identified with an impurity. It has been speculated that they are due to a moderate concentration of VHg TeHg frozen in because this complex has a slow diffusion rate. This study was done on HgTe and its relevance to HgCdTe alloys is only likely to correctly reflect their behavior at low Cd concentrations. Also VHg vacancies may become occupied by impurity atoms and become deep levels or resonant states. In addition, defect damage caused by ion implantation is also an interesting theme. All the impurities and defects affect electrical parameters in grown HgCdTe crystals (Bartlett et al. 1980; Dornhaus and Nimtz 1983; Capper 1989, 1991). An n-type HgCdTe alloy, with a low carrier density and a high mobility as well as a long minority carrier lifetime, is needed for a long-wave photoconductive detector working at 77 K (Willardson and Beer 1981; Keyes 1977). The impurities in HgCdTe have a critical influence on carrier lifetimes and mobilities. High impurity densities induce numerous recombination centers in the material, which drastically reduces the minority carrier lifetime. Ionization impurities and neutral impurities scatter carriers and depress the mobility. Therefore, it is very important to reduce the impurity density in HgCdTe crystals. Yet, to obtain photovoltaic devices with stable electrical properties, the HgCdTe material needs to be intentionally doped. A crucial step in fabricating HgCdTe focal-plane devices is to make p–n junction arrays in the active region of HgCdTe, by using ion implantation (Wang et al. 1991), diffusion methods, or by in-situ doping during MBE growth. Typically In ions are implanted, which manifest donor characteristics (Destefanis 1985; Schaake 1986; Vodop’yanov et al. 1982a, b), into p-type HgCdTe substrates to realize p–n junctions. While VHg are acceptors, they also are more effective scatters and life time

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killers than As-doped material, as long as the As can be placed on Te sites. Because As is amphoteric and is a donor when substituted on a Hg site, in LPE growth to locate it on a Te site it must be grown from the Hg side of the existence curve where the Hg vacancy density is a minimum (Berding et al. 1997). MBE growth always produces material at the Te side of the existence curve, and therefore as-grown, As resides mostly on the Hg sites. To get it to transfer to the Te sites requires a complex annealing procedure (Berding et al. 1998b). HgCdTe is a semiconductor material whose electrical properties are dominated by alloy composition and native point defects. If in the intrinsic, or even extrinsic, region of HgCdTe material the minority carrier lifetime is mainly determined by Auger recombination, the material is considered to be of high purity. For highpurity HgCdTe, the electrical parameters depend on the composition and the density of point defects associated with the stoichiometry deviation. Once the composition is fixed, it is possible to control the density of point defects, and hence the electrical parameters of HgCdTe crystals, by optimizing the heat treatment condition (Tang 1974, 1976). For high-purity HgCdTe bulk material, good agreement has been established for electrical parameters between theory and experiment. In Figs. 2.29 and 2.30, composition-dependent electron density and mobility are illustrated for highpurity n-type HgCdTe at 77 K (Higgins et al. 1989). It is clear that the electron density is about 6–15  1013 cm3 and the electron mobility is 3–5  105 cm2 =Vs. Figure 2.31 depicts the lifetime of minority carriers as a function of temperature for a HgCdTe sample (Kinch and Borrello 1975). The lifetime of the minority carriers is approximately 4–6 s at 77 K.

Fig. 2.29 Composition dependent carrier density of a high-purity n-type HgCdTe bulk crystal

2.2 Shallow Impurities

49

Fig. 2.30 Composition dependent carrier mobility of a high-purity n-type HgCdTe bulk crystal

Fig. 2.31 Lifetimes of minority carriers as a function of temperature for a high-purity n-type HgCdTe bulk crystal

2.2.2 Shallow Donor Impurities Because for low x values the band gap of Hg1x Cdx Te is narrow, the donor ionization energy is very small. For example, for a Hg1x Cdx Te sample with x  0:2, its band gap energy is Eg  0:1 eV, and correspondingly, for shallow donors its ionization energy Ed is only about 0:5 meV. This small energy is very difficult to deduce from a conventional Hall measurement. Shallow donor levels in

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Fig. 2.32 Magneto-transmission spectra of two n-type Hg1x Cdx Te samples at different temperatures (The arrows indicate two absorption peaks.) respectively. They are n-type doped with carrier densities of 3  1013 cm3

HgCdTe usually nearly coincide with the bottom of conduction band, and hence it is also impossible to investigate the impurity optical transition from its ground to excited state using photothermal ionization photoconductivity spectroscopy, a technique that has had great success in studying high-purity Ge material. Indeed, it is an interesting question to determine if the shallow donor levels can be separated from the bottom of the conduction band. Therefore, it is meaningful to study the magnetic freeze-out effect of the shallow donors at low-temperature. ICR facilitates this kind of study. Figure 2.32 depicts the conduction band electron cyclotron resonance spectra and ICR for two Hg1x Cdx Te samples in magnetic fields (Goldman et al. 1986). The compositions of the samples are x D 0:204 and 0.224, and the thicknesses are 290 and 260 m, and 6  1013 cm3 , and carrier mobilities of 2:7  105 cm2 =Vs and 1:2  105 cm2 =Vs, respectively, at a temperature of 77 K. The laser energy used is 10.44 meV. In these magnetic fields the conduction band electrons are quantized, leading to the formation of a series of Landau levels. As the magnetic field grows from 0, the energetic separation between the ground state Landau level, 0C , and the first excited Landau level, 1C , increases. When the energy separation becomes equal to the incident photon energy of the laser, a resonant absorption of the light takes place, and results in an absorption peak in a magneto-transmission spectrum, which is denoted as “CCR” in Fig. 2.32. Another absorption peak is also observed, that is caused by the impurity electron transition from the ground to the first excited state, and occurs at slightly lower magnetic field marked “ICR” in Fig. 2.32. The energetic separation between the CCR and ICR is given by EB D .E110  E000 /  .E1C  E0C /:

(2.47)

2.2 Shallow Impurities

51

This expression can be derived from: ˇ d.E1C  E0C / ˇˇ EB D  .BCCR  BICR / ˇ dB BDBCCR

(2.48)

where E1C and E0C represent the Landau levels of 1C and 0C respectively, and are functions of B. It can be either theoretically calculated or experimentally evaluated. Experimentally, the absorption peaks will appear at different magnetic fields if far infrared laser light with different energies, „!, are used as the excitation source. Figure 2.33a plots the relation between the values of „! and B at which the CCR and ICR absorption peaks occur. The curves are obtained using a Bowers– Yafet model (Bowers and Yafet 1959) with the conduction band bottom effective mass used as a fitting parameter. It is also possible to connect the experimental points into two smooth curves for the two different composition samples. Then ˇ d.E1C  E0C / ˇˇ . By multiplying the slope of the curves at B D BCCR is ˇ dB BDBCCR BCCR –BICR , the energy difference EB of the two transitions is obtained. The relation between B and EB is shown in Fig. 2.33b. The shallow impurity ionization energy can be obtained by extrapolating the curves to B D 0, and is approximately 0.3 meV. The theoretical values for the samples of x D 0:204 and 0.224, on the other hand, are 0.25 and 0.38 meV, respectively, according to an effective Rydberg energy calculation.

Fig. 2.33 (a) Resonance magnetic fields at several different photon energies („!). The curves are nonparabolic fits to the 0C ! 1C transition, with the effective mass as a fitting parameter. The inset shows the relevant energy-level scheme. (b) The energy splitting  D „!ICR  „!CCR vs. magnetic field (B) for two Hg1x Cdx Te samples with x D 0:204 and 0.224, respectively

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Fig. 2.34 Hall coefficients of an n-type InSb sample vs. temperature measured at different magnetic fields

A similar magnetic freeze-out phenomenon was also observed in InSb at lowtemperature (Sladek 1958). In Fig. 2.34, the Hall coefficients of n-type InSb are plotted as a function of temperature from 10 to 1.6 K for different magnetic fields. It is clear that as the magnetic field gets higher, the Hall coefficient shows a sudden decrease above a critical temperature, which suggests a sudden reduction in the carrier density. The reason is that the electrons in the conduction band freeze-out as the donor levels deepen at the higher the magnetic fields. At a low-temperature, the frozen-out electrons may be re-excited into the conduction band by an electric field. Figure 2.35 illustrates such a case for n-type InSb in a magnetic field of 29 kilogauss at a temperature of 2.45 K. A drastic decrease of the Hall coefficient occurs as the electric field increases from zero to about 1 V cm1 , indicating a rapid increase of the carrier density in the conduction band as the electron distribution is heated by the electric field. Chen et al. have observed the magnetic freeze-out effect of donor impurities by measuring the field-dependence of the electron temperature’s impact on the electrical conductivity in HgCdTe (Chen 1990). The electrical conductivity shows a sharp jump at higher magnetic fields that is attributed to impact ionization induced by the electric field. Not surprisingly the higher the magnetic field, the larger the electric field required to initiate the jump of the electrical conductivity. This occurs because the magnetic-induced Landau level deepens as the magnetic field gets higher, resulting in an increase of the impurity ionization energy. Zheng et al. have also studied the transport behavior of the electrons associated with localized shallow donor levels in wider gap Hg0:58 Cd0:42 Te (Zheng et al. 1994). The result is illustrated in Fig. 2.36. At zero magnetic field the data indicates

2.2 Shallow Impurities

53

Fig. 2.35 The Hall coefficient as a function of electric field for an n-type InSb sample measured at different magnetic fields

Fig. 2.36 Conductance vs. electric field for a Hg0:58 Cd0:42 Te sample in different magnetic fields

no evidence for a magnetic freeze-out effect of the donor levels. In general, impurity atoms are assumed to be completely ionized in HgCdTe at 77 K because the donor levels are quite shallow, nearly degenerate with the bottom of the conduction band. Therefore, the carrier density determined by measuring the Hall coefficient of a sample at 77 K can be taken as the effective donor concentration ND . The carrier density at any temperature can be easily calculated by using the relation ni 2 D n.n  ND  /. The Fermi energy can also be deduced from the distribution of electronic states in the conduction band. Figure 2.37 depicts the Fermi levels of Hg1x Cdx Te samples (x D 0:194) as a function of temperature with different donor concentrations. It is clear that the location of actual Fermi energy relative to the bottom of conduction band varies with an increase of temperature from 77 to 300 K, and gradually approaches the intrinsic Fermi energy as the temperature gets close to room temperature. The Fermi energy is higher for higher effective donor concentration, and this effect is most significant at low-temperature.

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Fig. 2.37 Fermi energy levels of a series of HgCdTe samples (x D 0:194) with different donor concentrations. curve 1: ND D 2:2  1016 cm3 , curve 2: ND D 1  1016 cm3 , curve 3: ND D 2:26  1015 cm3 , and curve 4: intrinsic condition

2.2.3 Shallow Acceptor Impurities Shallow acceptor levels in HgCdTe pose an interesting problem. For unintentionally doped HgCdTe, the shallow acceptor levels observed are mainly due to Hg vacancies. The energy position of Hg vacancy is usually experimentally determined. Scott et al. (1976) have carried out Hall, far infrared transmission, and photoconductivity measurements on p-type Hg1x Cdx Te samples with x D 0:4 and doping concentration p D 4  1015 , and 1  1017 cm3 . In the photoconductivity measurement, a sharp peak occurs at 13.4 meV. In the far infrared transmission spectrum recorded at 8 K, a sharp absorption peak also appears at about 13.4 meV .107 cm1 /, as illustrated in Fig. 2.38. This absorption peak was also evidenced in transmission measurements (Shen 1994). According to experimental electrical results, a simple relation can be established between the shallow acceptor ionization energy and the hole density at 77 K (Scott et al. 1976), (2.49) EA D E0  ˛p01=3 where E0  17 meV, ˛ D 3  108 eV cm and p0 is the hole density at 77 K. Similar results of E0  17:5 meV, ˛ D 2:4  108 eV cm have also obtained by Hall measurements and corresponding fitting procedures (Yuan et al. 1990). Li Biao et al. have published a direct experimental result for the Hg vacancy energy level (Li et al. 1998) from a far infrared spectrum. For a thick sample, it was found to be very difficult to separate the shallow acceptor levels from reststrahlen spectra and two-phonon absorption bands, because the shallow acceptor energies vary from 1 to 30 meV (or equivalently, 10–250 cm1 ), which are very close to the reststrahlen spectra energies and two-phonon absorption bands. For a sample grown by MBE or LPE, however, the thickness is very thin, making it possible to investigate the shallow acceptor levels by far infrared absorption measurements. The samples studied are 20-m-thick undoped and Sb-doped materials prepared by LPE,

2.2 Shallow Impurities

55

Fig. 2.38 The transmission spectrum of a Hg0:6 Cd0:4 Te sample at a temperature of 8 K

Fig. 2.39 Far infrared transmission spectra of the HgCdTe epitaxial layers at 4.2 K. curve 1 is the p-type MBE thin film (x D 0:285), curve 3 and curve 2 are the transmission spectra of a before annealing p-type (x D 0:37) and an after annealing n-type LPE sample, respectively

and 10-m-thick thin films prepared by MBE. The hole density falls in the range 1  1015  7  1016 cm3 . The measured spectroscopic range is 20–250 cm1 . Figure 2.39 shows typical far infrared transmission spectra measured at a temperature of 4.2 K. The absorption peak marked with BSR is an feature related to the beam splitter. Curve 1 is an absorption spectrum of a p-type HgCdTe .x D 0:285/ sample grown by MBE. It has an absorption peak, marked with VHg , clearly seen at 92 cm1 , or equivalently at 11.4 meV. Curve 3 is a far infrared absorption spectrum of a p-type HgCdTe .x D 0:37/ sample grown by LPE. It has an obvious absorption peak, marked with VHg , at 86 cm1 , or equivalently at 10:6 meV. Curve 2 is the far infrared transmission spectrum of the LPE sample after an n-type conversion annealing treatment. The annealing changes the sample from p-type to n-type. It is clear that the absorption peak previously appearing at 86 cm1 in curve 3, is missing in curve 2. Further measurements indicate that the intensity of the absorption peak does not show a drastic decrease as the temperature increases. All these findings suggest that the absorption peak is not due to lattice absorption but are caused by Hg vacancies. Figure 2.40 illustrates the results of Hall measurements and integrated absorption intensities (IAI) as well as absorption pair-peak heights (PPH) for a p-type sample prepared by LPE, and measured at different temperatures. From the Hall

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Fig. 2.40 The hole density (Hall measurement), integrated absorption intensity (IAI) and pair-peak height (PPH) at different temperatures for a p-type Hg0:63 Cd0:37 Te sample. The inset gives the far infrared transmission spectra at different temperatures

curve the ionization energy EA and the concentration of the Hg vacancies NA are found to be 9.7 meV and 7:6  1014 cm3 , respectively. The ionization energy value is close to the result obtained by absorption spectroscopy. It is clear that as temperature decreases, the PPH and IAI increase and the hole concentration decreases, indicating the presence of a carrier freeze-out effect. On the assumption that the Hg vacancy concentration is proportional to the IAI, a relation can be deduced (Klauer et al. 1992): R ˛ dv (2.50) CVHg D aVHg ln 10 where aVHg is the absorption strength per Hg vacancy. From the Hall measurement, NA D 7:61014 cm3 , and from the absorption spectrum, it R is deduced that CVHg3  2 ˛dv D IAI D 610 cm . Therefore, the result derived is aVHg  3:41012 cm. This value is very important for estimating the positively charged vacancy concentration. For example, for the undoped MBE sample involved in Fig. 2.39, the vacancy concentration is estimated to be 3:8  1014 cm3 by multiplying absorption area with absorption strength per Hg vacancy, and is similar to the Hall data result, 5:5  1014 cm3 . Figure 2.41 depicts the Hg vacancy ionization energies EA of LPE grown p-type and MBE grown n-type samples with different compositions. Obviously, most of the samples manifest ionization energies around 10–12 meV, independence of the composition. This value is close to the result obtained by Sasaki et al. (1992) on MBE samples, and that by Shin et al. (1980) on LPE samples. However, theoretical calculations suggest that the ionization energy of the Hg vacancy depends on the forbidden band gap Eg . The discrepancy may be introduced by the influence of a longitudinal compositional distribution, or an interface lattice mismatch, that affect the acceptor levels of HgCdTe epilayers. No absorption peak is observed from As impurities in As-ion-implanted HgCdTe samples. The reason is that the As impurity is amphoteric leading to highly compensated material with the As mostly residing on the cation sublattice where it

2.2 Shallow Impurities

57

Fig. 2.41 The Hg vacancy ionization energies EA of HgCdTe LPE grown and MBE grown samples with different compositions, obtained from far infrared absorption spectra at 4.2 K Fig. 2.42 The magnetooptical far infrared spectra of an Hg0:63 Cd0:37 Te sample prepared by LPE and measured at a temperature of 4.2 K

is a shallow donor (Berding et al. 1997; Berding and Sher 1998a). For Sb-doped Hg1x Cdx Te .x D 0:39/ samples prepared by LPE, besides the Hg vacancy absorption that appears at 87 cm1 , an additional absorption peak is at 83 cm1 , or equivalently, 10.5 meV, which is Sb impurity related. This is consistent with the reported value of 11 meV for the acceptor level of Sb-doped Hg1x Cdx Te .x D 0:22/ samples (Chen and Dodge 1986). Figure 2.42 plots the magneto-optical far infrared spectra of acceptor states in HgCdTe at a temperature of 4.2 K. Due to the Zeeman effect, the excited states of the Sb impurity and the Hg vacancy split in magnetic fields. In Fig. 2.43, the Zeeman splitting is plotted as a function of the magnetic field. The energy positions of acceptor levels can also be investigated by PL spectroscopy. Richard and Guldner et al. have performed PL measurements on

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Fig. 2.43 The Zeeman splitting as a function of magnetic field for the Sb acceptor state in a Hg0:63 Cd0:37 Te sample

Hg1x Cdx Te samples (x D 0:285) at a temperature of 18.6 K by using a CO laser as the excitation source. The excitation energy is 244.6 meV, and the power is 140 mW. Recombination emission from the conduction band to acceptor levels have been observed, with  D 3:2 meV, Eg EA D 202:7 meV. Because EA D 14:3 meV, we find Eg D 217 meV. Kurtz et al. (1993) have measured infrared PL spectra of Hg1x Cdx Te samples prepared by MOCVD .x D 0:216/ and by LPE .x D 0:234/, respectively, by using a double-modulation (DM) technique. In Fig. 2.44, the PL spectra are depicted for the samples before and after an annealing process. Before annealing, the PL peak reflects the recombination processes between the conduction band and acceptor levels, and reveals several Hg vacancy acceptor levels. The band-edge PL peak is relatively broad and appears at a higher energy. After annealing in a Hg atmosphere, the Hg vacancies are removed and the PL peak reflects the luminescence of radiation from conduction band to valence band recombination. The full-width at half-maximum (FWHM) of this band-edge PL peak is relatively small, and appears at a higher energy. The Hg vacancy acceptor level is found to be 12 and 19 meV for Hg1x Cdx Te samples with x D 0:216 and 0.234, respectively. From the measurements, the Hg vacancy acceptor level is found to lie in the range of 10–15 meV above the valence band edge and it moves down to the valence band edge as the acceptor concentration increases. According to Scott the relationship is EA D 0 for NA  3:2  1017 cm3 . Therefore, the PL peaks of the conduction-band to acceptor levels are expected to show a blue shift with an increase of the acceptor concentration. Hunter and McGill (1981) have measured the PL spectra of two Hg1x Cdx Te samples with x D 0:32 and 0.48, and observed recombination emissions of the conduction band to valence band, between acceptor levels, the donor to acceptor levels, and among bound excitons and other levels. Both the line shape and the intensity of the conduction band-valence band transition depend on the excitation power. Figure 2.45 illustrates a PL spectra of a Hg1x Cdx Te.x D 0:48/ sample at

2.2 Shallow Impurities

59

Fig. 2.44 Photoluminescence (PL) spectra of two HgCdTe samples prepared by MOCVD (a) and LPE (b), measured before and after an annealing process

Fig. 2.45 The PL spectra of a Hg0:52 Cd0:48 Te sample measured at 4.6, 9.3, 18.8 and 30 K, respectively

different temperatures. The peak at the lower energy is due to the recombination between the conduction band and acceptor levels for T > 10 K, and between the donor and acceptor levels at lower temperature. The peak at high energy corresponds to the PL transition between the conduction and valence band, and the middle

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2 Impurities and Defects

Fig. 2.46 The PL peak energy as a function of temperature for an Hg0:52 Cd0:48 Te sample at different temperatures

peak position is due to the transition with bound excitons (especially obvious at T D 9:3 K). In Fig. 2.46, the PL peak energy is plotted as a function of temperature for a Hg1x Cdx Te sample with x D 0:48. It can be determined from the PL peak energy that the acceptor ionization energy, EA , is 14:0 ˙ 1:5 meV for x D 0:32 and 15:5 ˙ 2:0 meV for x D 0:48. The donor ionization energy, ED , is also obtained to be 1:0 ˙ 1:0 meV for x D 0:32 and 4:5 ˙ 2:0 meV for x D 0:48. The acceptor may be an Au-substitutional impurity on a cation site or a cation vacancy. The experimental acceptor ionization energy of an Sb-doped HgCdTe sample is slightly smaller than that of the Hg vacancy. Chen et al. (1990) and Li et al. (1998) reported a value of about 10 meV. Smaller values were also reported. For example, Wang (1989) has studied a series of Sb-doped HgCdTe bulk crystal samples. The samples became p-type after a conventional Hg-saturated, n-type anneal. The Hg vacancy concentration is Sb independent, and can be deduced from the relation between the Hg vacancy concentration and the heat treatment, to be 1014 cm3 . Meanwhile, the p-type doping due to the Sb concentration is larger than 1015 cm3 . The reason for the p-type characteristic of an Sb-doped HgCdTe sample after lowtemperature processing is that Sb atoms replace the Te in the lattice (Berding et al. 1997; Berding and Sher 1998a), or are in interstitial sites, where they are acceptors. The Hall coefficient, electric conductivity, and mobility of the samples have been measured. In the low-temperature ionization region the resistivity can be expressed as: (2.51)  / T 3=4 e .EA =2kB T / ; therefore, the slope of a ln.T 3=4 /  1=T curve gives the acceptor ionization energy EA . The acceptor ionization energies determined with this method are listed in Table 2.7 for a series of Sb-doped Hg1x Cdx Te samples.

2.3 Deep Levels

61

Table 2.7 The acceptor ionization energies of p-HgCdTe Acceptor P .cm3 / type x EA .meV/ Sb 0.36 6 3:2  1016 Sb 0.21 7 6  1016 Sb 0.22 2 7:2  1016

Sb Sb VHg

0.22 0.39 0.26–0.33

11 10.5 15–18

7:6  1014 5  1016

VHg

0.32–0.48

15

1016

VHg

0.20–0.39

11.5

7:6  1014

Reference Wang (1989) Capper et al. (1985) Gold and Nelson (1986), Chen and Tregilgas (1987) Chen and Dodge (1986) Li et al. (1998) Capper et al. (1985), Chen and Tregilgas (1987) Hunter and McGill (1981) Li et al. (1998)

2.3 Deep Levels 2.3.1 Deep Level Transient Spectroscopy of HgCdTe A deep level is an energy state located in the forbidden band near the center of the gap that is produced by the short-range primitive cell potential of a defect center. The defect can be due to an impurity, a native point defect, a complex of native point defects, or a complex of a native point defect with an impurity. The deep level can capture holes or electrons and hence acts as an electron/hole trap. It reduces carrier lifetimes to affect device performance. To study the deep energy levels of defects in bulk material, a junction space charge technique is often adopted. The optical methods (Hall, PL, absorption, and PTIS) have an obvious advantage of high spectral resolution, which is very helpful for exact determination of the energy positions of defect levels. However, they cannot determine accurate information about other electrical parameters impacting the carrier density, and the capture and the emission rates. The junction space charge method has a lower spectral resolution, about 10 meV, but it can be used to get the absolute value of the electrical parameters. One major junction space charge method effective in studying the deep levels in HgCdTe, is DLTS. Other experimental methods besides the DLTS, that can be used in the study of deep levels include, admittance spectroscopy (AS), low-frequency conductance spectroscopy (LFCS), and thermally stimulated current (TSC). DLTS was first established in 1974 (Lang 1974). It is an effective method for studying deep levels in semiconductors. With this method, different parameters can be measured, which include the concentration of deep level traps (NT ), the energy levels of the deep level traps (Et ), the electron or hole capture cross section ( ),

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2 Impurities and Defects

Fig. 2.47 A schematic of the deep level transient spectroscopy (DLTS) setup

the optical cross section ( o ), the distribution of random traps in the diode junction area (NT .z/), and the carrier emission rate of traps. One can also distinguish if the trap captures majority or minority carriers. The schematic configuration for DLTS is plotted in Fig. 2.47. Samples that can be measured by DLTS include a Schottky potential barrier diode, an MOS device, or more generally any structure for which a depletion layer can be established. For an nC -p photoelectric diode in reverse bias, the depletion layer is mainly on the p side of the diode. The sample is placed in a variabletemperature cryostat and its capacitance is measured with a fast capacitance bridge. The sample is first set in reverse bias for a long enough time to ensure the equilibration of a depletion layer in the p region. In the depletion layer any carriers captured in the traps are removed and thus the traps are initially empty. Now two operations are performed. One operation is to apply a pulse signal with its height being smaller than the reverse bias voltage, so that even at the pulse maximum the device is still in reverse bias, as illustrated in Fig. 2.48. Under the influence of the pulse, some holes return to the depletion layer in the p region, while others return after the pulse is over. A few holes will be captured in this process by the traps in the depletion layer. The other operation is to apply a pulse signal with its height higher than the reverse bias voltage. As the pulse reaches its maximum, the device will be driven into forward bias, so that not only holes, but also electrons are swept into the depletion layer of junction region. After the pulse, the holes/electrons will be captured if there are corresponding traps in the region. Obviously, hole traps can be detected in the first operation, while in the second operation the hole and electron traps can be detected together. By combining the two operations, the behavior of the electron and hole traps can be distinguished. After the pulse, the electrons or holes trapped in the deep level traps can via thermal excitation return to their equilibrium from the initial nonequilibrium condition. This gives rise to a capacitance transient of the device whose response is determined by the thermal emission rates of electrons or holes in the traps, the temperature, and the location of the deep levels. Measuring the capacitance transients at different temperatures leads to a determination of the behavior of the corresponding

2.3 Deep Levels

63

Fig. 2.48 A schematic of the capacitance transient change caused by the emission of the trapped carriers

deep level traps. The capacitance transient of deep levels as a function of temperature is determined experimentally mainly by measuring the transients due to thermal emission rates of the trapped electrons and/or holes, and is related to a space-charge dynamical process of capture and thermal emission. If the depletion layer of an nC -p junction lies on the p-region side, and is steplike with the thickness W , then the junction capacitance can be expressed as: C.t / D

A" D W



A2 q" NI 2.Vbi C VR /

1=2 ;

(2.52)

where A is the junction area, Vbi is the build-in electric potential of the junction, VR is the applied reverse bias voltage, and NI D NA –ND is the net density of charge centers in the p-type depletion layer. The maximum electric field jFm j across the

64

2 Impurities and Defects

junction is: Q=C.t / qNI W V D D : (2.53) W W " Since the electric field jFm j is normally very strong, the thermally excited carriers will be swept out of the space charge layer very rapidly, and because the trap capture rates are comparatively slow it is safe to assume that the swept-out carriers will not be re-captured by the traps in this process. The capture rates of electrons and holes can be expressed, respectively, as: jFm j D

Cn D n hvn i n; ˝ ˛ Cp D p vp p;

(2.54) (2.55)

˝ ˛ where n and p are capture cross sections, n and p the densities, and hvn i and vp the average thermal velocities of electrons and holes. These average velocities are determined by: ˝ ˛ vp D



 hvn i D

8kB T  mhh 8kB T  m

1=2 ;

(2.56)

;

(2.57)

1=2

where m and mhh are the electron and hole effective masses. In thermal equilibrium, the thermal emission rate of each electron state is equal to the corresponding capture rate. According to Boltzmann statistics, the emission rates for electrons and holes are: en D .n hvn i =gn /Nc e .E=kB T / ; ˝ ˛ ep D .p vp =gp /Nv e .E=kB T / ;

(2.58) (2.59)

where gn and gp are the ground state degeneracy factors of the electron and the hole traps, with gp D 4, and gn D 2, and: E D Ec  Et

.for electrons/;

(2.60)

E D Et  Ev

.for holes/:

(2.61)

For a deep level trap that can capture and emit electrons and holes, the following expression holds: dN.t / D .Cn C ep /.NT  N.t //  .Cp C ee /N.t /; dt

(2.62)

2.3 Deep Levels

65

where NT is the total defect concentration, N.t / the defect concentration occupied by electrons, and NT N the defect concentration occupied by holes. By assuming  a D Cn C ep D n ˝hvn˛i n C ep ; (2.63) b D Cp C en D p vp p C en ; Equation 2.62 can be simplified further. For a trap filled with electrons at initial time t D 0, that is N.0/ D NT integrating (2.62) leads to: 8 0/: aCb

(2.64)

Correspondingly, for a trap filled with holes at the initial time t D 0, the integration becomes: 8 <0 .t 6 0/ ˚ N.t / D : (2.65) a Œ.aCb/t : NT 1  e .t > 0/ aCb For either of the two cases, one finds from (2.64) to (2.65) for t ! 1: N.t ! 1/ D

a NT ; aCb

(2.66)

which is the highest occupied steady-state concentration of a trap that can be reached for a given trap energy level. Figure 2.49 presents the DLTS spectra of a p-type Hg1x Cdx Te .x > 0:215; NA D 9:1  1015 cm3 / photodiode (Polla and Jones 1981). The lower spectrum was measured with the photodiode in reverse bias, VR D 0:60 V, and the applied

Fig. 2.49 DLTS spectra of a p-type Hg0:785 Cd0:215 Te photodiode, where single hole- and electron-traps can be detected

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2 Impurities and Defects

pulse voltage, Vpulse , is VR C 0:50 V, with a pulse width of 5 s. It is equivalent to the first operation mentioned above, and only the capture of holes is observed. A hole–trap related absorption peak obviously appears at a temperature of 32 K, with an emission time constant of 55 s. The upper spectrum is a measurement for an applied pulse voltage of Vpulse D VR C 0:80 V. In this range of pulse times, the diode is just in forward bias. And neither electrons nor holes can enter the depletion region. Clearly an electron–trap related peak occurs at a temperature of 27 K, with an emission time constant of 182 s. The peak will change its position on the temperature axis with the pulse width that is either higher or lower with a spectrum illustrated in Fig. 2.49. From (2.58) to (2.59), the reciprocal of the thermal emission rate is the ˝ ˛ time constant ( ), and both the hvn i and vp are proportional to T 1=2 , while Nc and Nv are proportional to T 3=2 , as shown in (2.67) and (2.68), 

mc kB T Nc D 2 2„2 

mhh kB T Nv D 2 2„2

3=2 ;

(2.67)

3=2 :

(2.68)

Therefore, we have: .kB T /2 mhh e E=kB T 1 D ep D p ;

e 2 2 „3

(2.69)

. e T 2 / / e .E=kB T / :

(2.70)

and It is obvious that by drawing a straight line in the ln. T 2 /  1=kT coordinates, the slope of the lines, E D Ec  Et or E D Et  Ev can be determined. In Fig. 2.50, the corresponding curves are given for the sample shown in Fig. 2.49, from which the hole and electron traps are determined to be at Et D Ev C 0:035 eV and Et D Ec  0:043 eV D Ev C 0:043 eV, respectively. The traps will not have enough time to capture carriers if the injection pulse time is very short. Meanwhile, most of the traps will not stop capturing carriers until saturation is reached if a wide injection pulse is applied. This leads to an exponential increase of the DLTS spectrum: A.t / D Amax Œ1  e.t=/ :

(2.71)

Figure 2.51 depicts experimental results for an Hg1x Cdx Te sample with x D 0:215 reported by Polla and Jones (1981). For t D 0; A.0/ D 0; and for t D 1; A.1/ D Amax is saturated. Therefore, one finds:   t Amax  A.t / (2.72) D : ln Amax

2.3 Deep Levels

67

Fig. 2.50 Activation energies of the hole- and electron-traps calculated from the peak values illustrated in Fig. 2.49 Fig. 2.51 Capture cross sections of minority and majority carriers determined by the peak value of the DLTS spectra in Fig. 2.49

For the hole traps, the expression is: ˝ ˛ 1 D p vp p:

p

(2.73)

The ln.ŒAmax –A.t /=Amax /  t plot is a straight line, and from its slope, p D

˝ ˛ 1 p vp p is determined, which is the time needed to fill the traps fully. From

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2 Impurities and Defects

Fig. 2.52 Filling time constants of the majority carriers determined from the experimental results illustrated in Fig. 2.51

˝ ˛ the thermal velocity vp and the hole density p, the capture cross section p can also be obtained. Figure 2.52 depicts the experimental relation between ln.ŒAmax  A.t /=Amax / and t for the sample shown in Fig. 2.50. It can be easily derived from the slope that p and p for the hole traps at 30 K are 7:9107 s and 3:11017 cm2 , respectively; and p for the electron traps is 2:1  1015 cm2 . The capture cross sections of the traps are temperature independent. Polla and Jones (1981) have employed this method in studying deep level spectra of undoped and Cu- and As-doped samples. Figure 2.53 plots the DLTS spectra of intrinsic Hg1x Cdx Te.x D 0:39/ and a Cu-doped one, respectively (Jones et al. 1982). The hole density of the undoped sample is p  1  1016 cm3 . With an increase of the forward-bias voltage, the electron trap signal appearing at 150 K disappears gradually, and the electron trap signal at 45 K get stronger. The electron traps at these two temperatures suggest the assignments EC 0:1 eV and EC 0:24 eV, respectively. Under reverse bias, a trap at EV C 0:28 eV shows up. For the Cu-doped sample illustrated in Fig. 2.53b, two Cu impurity-related traps are observed at 0.07 and 0.15 eV, respectively, above the top of the valence band. These deep level locations are concentration dependent, and the dependence is shown in Fig. 2.54. For the undoped Hg1x Cdx Te.x D 0:2–0:4/ samples, the deep center levels are located at EV C 0:4Eg and EV C 0:75Eg in the forbidden band, respectively. The reported deep levels of CdTe are at EV C 0:15 eV and EV C 0:36 eV, respectively (Zanio 1978), which are also depicted in the figure.

2.3 Deep Levels

69

Fig. 2.53 DLTS spectra of undoped and Cu-doped HgCdTe samples. The electron traps decrease to zero at 150 K and increase with the forward-biased voltage at 40 K

The DLTS measurements also provide information on the electron and hole capture cross sections of the deep level centers. For the undoped Hg1x Cdx Te (x D 0:2  0:4) samples, the electron and hole capture cross sections are n  1015  1016 cm2 and p  1017  1018 cm2 for the energy level at EV C 0:4Eg , and n  1016 cm2 and p  1017  1020 cm2 for the deep level at EV C 0:75Eg , respectively. For the Cu-doped Hg1x Cdx Te.x D 0:39/ sample, the values are n  1016 cm2 and p  1018  1019 cm2 , respectively.

2.3.2 Deep Level Admittance Spectroscopy of HgCdTe This technique is an important supplement to the thermal excitation current spectroscopy, thermal excitation capacitance spectroscopy, frequency swept conductance spectroscopy, and DLTS, and is suitable for narrow band semiconductors.

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2 Impurities and Defects

Fig. 2.54 Trap energy as a function of composition determined by DLTS measurements for an undoped (a) and Cu-doped (b) HgCdTe samples. The right-hand side is the value of CdTe according to Zanio (1978)

It is used mainly to measure the change of admittance with temperature (Losee 1972, 1975) but also details of the interface structure between the insulator and the active material (Tsau et al. 1986; Sher et al. 1983). For an nC -p junction containing deep levels, the conductance GT is: GT D Œep ! 2 =.ep2 C ! 2 /.NT =p/C0 ;

(2.74)

where NT is the concentration of the deep levels; ! the angular frequency of the driven electric current; p the carrier density, and ep the hole thermal emission rate, which is given by: ˝ ˛ (2.75) ep D q 1 p vp Nv eŒ.Ev Et /=kB T  : ˝ ˛ In this expression q (q D 4) is the degeneracy of the trap ground state, vp is the average hole thermal velocity, p is the hole capture cross section, N is the effective density of states of the valence band, E is the energy of the top of valence band; Et is the trap energy, C0 is the high-frequency junction capacitance determined by: C0 D "A=W;

(2.76)

where " is the dielectric constant of the semiconductor, A the area of the junction, and W is the width of the depletion layer. When the deep level response can follow the alternating signal, there is an additional capacitance CT , CT D Œep2 =.ep2 C ! 2 /.NT =p/C0 : The total capacitance of the junction C is therefore C0 C CT .

(2.77)

2.3 Deep Levels

71

Fig. 2.55 The conductance as a function of temperature for a Hg0:695 Cd0:305 Te photodiode measured at different frequencies

If both the p and C0 change little with temperature, the temperature dependence of the admittance is determined mainly by ep .T /. GT will hence reach its maximum when ep D !. 1 GT jmax D !.NT =p/C0 : (2.78) 2 If C0 and p are obtained from C –V and Hall measurements, respectively, then NT can be deduced from (2.78). Changing ! will produce a set of maximum values occurring at different temperatures. Figure 2.55 illustrates the relation between the conductance and the temperature at different frequencies (Polla and Jones 1980a). The acceptor concentration NA is 4:8  1016 cm3 . Each curve has a maximum, which corresponds to a temperature determined ˝ ˛ by ! D ep .T /. The thermal emission rate ep .T / is given by (2.75), where vp is proportional to T 1=2 , and Nv is proportional to T 3=2 . Thus from the relation: ˝ ˛ ! D ep D q 1 p vp Nv eŒ.Ev Et /=kB T  / T 2 eŒ.Ev Et /=kB T  ; (2.79) the slope of the ln.! 1 T 2 /  1=kT curve is deduced to be E D Et  Ev , from which the location of the deep level can be determined. In addition, it is obvious

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2 Impurities and Defects

Fig. 2.56 The trap activation energy determined from the conductance peaks in Fig. 2.55. The trap activation energy corresponds to a hole trap located at 0.16 eV above the top of the valence band

from (2.74) to (2.78) that C D C0 if ep .T1 / << !, and C D C0 C .NT =p/C0 if ep .T2 / >> !. Therefore, we find: C D .NT =p/C0 ;

(2.80)

where C is the change of the junction capacitance between the temperatures T1 and T2 , and C0 is the high-frequency junction capacitance. The deep level concentration NT can therefore be obtained from (2.80). From the slope of the straight line ln.! 1 T 2 /  1=kB T given in Fig. 2.56, the location of deep level is determined to be Et  E D 0:16 eV. The capacitance difference C between the two capacitance plateaus at temperatures T1 and T2 can be obtained from the capacitance-temperature curves measured at different frequencies, leading to a determination of NT D 4:4  1014 cm3 . From (2.75) the hole capture cross section in the temperature range between 130 < T < 200 K is 31016 cm2 . For a sample with x D 0:219 and NA D 9:11015 cm3 , it has been shown that NT D 2:3  1015 cm3 and Et D E C 0:046 eV, and the hole capture cross section is 7  1016 cm2 in the temperature range between 74 < T < 98 K. By using this technique, the hole density, its energy level, and the capture cross section of any p-type HgCdTe alloy can also be determined. Photon-modulation spectroscopy provides another pathway to investigate the deep levels in HgCdTe. The method adopts a dc probe light beam of tunable wavelength (Ep < Eg /, and a modulated light beam at frequency !.„! > Eg / but of fixed wavelength, and employs a lock-in technique to probe the change of the emission rate (Ip =Ip /. The modulation spectrum, Ip =Ip  Ep is then obtained by scanning Ep . Figure 2.57 shows a schematic of the experimental setup.

2.3 Deep Levels

73

Fig. 2.57 A schematic of the photon-modulation spectroscopy set up

Fig. 2.58 Ip =Ip as a function of the probe photon energy „!p at T D 49 K for Hg1x Cdx Te (x D 0:238 and 0.307) samples

Polla measured the deep levels in Hg1x Cdx Te.x D 0:24–0:37/ samples prepared by LPE using the photon-modulation spectroscopy method (Polla et al. 1982). The thicknesses of the samples were in the range between 15 and 40 m. They were placed in a variable-temperature cryostat. The pump light was from an ArC laser set at a wavelength of 514.5 nm and had a light intensity of 8:7 W=cm2 . The modulation frequency was 500 Hz. A Ge:Cu detector was used to sense the signal. The modulation transmission spectra measured at a temperature of 94 K are depicted in Fig. 2.58 for x D 0:238 and 0.307 samples, respectively. Three peaks, labeled A, B, and C, are present for all compositions, and their energies are plotted

74

2 Impurities and Defects

Fig. 2.59 Energy positions of peaks A, B, and C as functions of the composition for Hg1x Cdx Te samples. The dotted lines are the fits to the experimental data, and the solid line is calculated results by Schmit and Stelzer (1969)

Fig. 2.60 A schematic diagram of the optical transitions corresponding to the peaks A, B, and C

in Fig. 2.59. The peaks correspond to three optical transitions, whose initial states are shallow acceptor states (Scott et al. 1976), and their final states are donor-like deep levels in the forbidden band. Peak A is a transition from an acceptor level to a deep level (D1) in the middle of the forbidden band. Peak B is from an acceptor level to the deep level at 3=4Eg . And Peak C is from an acceptor level or the valence band edge to the conduction band. The alloy composition variations of these peaks are given in Fig. 2.59, and a schematic of their positions are in Fig. 2.60. From these results, the deep levels corresponding to the transitions of A and B are located at EV C 0:4Eg and EV C 0:75Eg , respectively, which are consistent with the Jones et al. results. It can therefore be concluded that these two deep levels are universal in HgCdTe. They may be the cation vacancy related defect states; the Kobayashi theoretical estimation which was mentioned in Sect. 2.1. The DLTS method has also been used to measure the deep levels of Au-doped samples that had no As dopants added. Cotton and Wilson (1986) have measured the trap energy levels of these n-type Hg1x Cdx Te.x D 0:3/ ion implanted samples with the DLTS method and found a defect-related trap energy level at Ec  0:19 eV with a very low density, 5  1021 cm2 . Chu using the DLTS method, has reported an electron trap at Ec 85 meV for a Hg1x Cdx Te.x D 0:313/ sample prepared by LPE.

2.3 Deep Levels

75

Huang et al. have systematically studied various deep levels of p- and n-type Hg1x Cdx Te samples with large Cd concentrations (Huang et al. 1988), and found that: 1. Two deep level traps are observed due to residual impurities in an n-type Hg1x Cdx Te.x D 0:403/ sample. They are acceptor-like electron traps locate at 0:3Eg and 0:5Eg , respectively, below the bottom of the conduction band. Their electron capture cross sections are 1:11017 cm2 at 130 K and 1:01016 cm2 at 172 K, and the concentrations are 0:61ND and 0:072ND , respectively. The n-type Hg1x Cdx Te sample with x D 0:804 manifests similar results. 2. Two deep level traps are observed in an undoped p-type Hg1x Cdx Te .x D 0:403/ sample. They are donor-like hole traps locate at 55 meV and 0:4Eg above the top of the valence band, respectively. Their hole capture cross sections are 1:0  1018 cm2 at 90 K and 7:3  1018 cm2 at 250 K, and their concentrations are 0:29NAD and 0:130NAD respectively. No deep level traps are observed at 55 meV above the top of the valence band in this p-type Hg1x Cdx Te.x D 0:361/ sample; only a deep level trap at 0:4Eg above the top of the valence band is observed. 3. The Hg1x Cdx Te samples grown by different methods have different types of deep levels, and hence different trap densities and locations, which significantly restrict the performance of the materials and detector devices.

2.3.3 Frequency Swept Conductance Spectroscopy LFCS is another powerful way to examine the interface and trap properties of HgCdTe alloy to insulator contacts (Tsau et al. 1986). Unlike DLTS which is a method that initially takes the sample well away from equilibrium and studies the transient as it returns, the LFCS method applies a varying gate voltage and at each voltage setting allows the sample to equilibrate. Then the frequency could be swept from 104 Hz to 10 MHz (Sher et al. 1983). At each frequency a 4 cycle sequence is done and the signal detected with an automatically tuned lock-in amplifier. Each 4 cycle sequence is repeated at least 100 times to improve the signal to noise ratio. This process is accomplished with two devices, a Solartron model 1250 that operates from 104 Hz to 10 KHz and an H-P model 4,061 A semiconductor testing system, a frequency response amplifier that operates from 10 KHz up to 10 MHz. The lowest frequency used in this experiment was 102 Hz so there were eight decades of frequency employed. When this method was applied to an Si=SiO2 interface (Sher et al. 1983) the usual U-shaped density of states observed in the band gap was decomposed into conduction and valence band tails that were observed to hybridize where they crossed near the center of the gap. In addition deep state traps were identified and characterized. This method was applied to a Hg0:7 Cd0:3 Te sample with a 1,660 A thick Photox SiO2 layer deposited on its surface to form an MIS device structure (Tsau et al. 1986). The metal gate was made up of a thin 400 A thick layer of Ti, followed

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2 Impurities and Defects

Fig. 2.61 The effective series capacitance vs. gate voltage for several frequencies

by 4,000 A of Au. The sample was n-type with a carrier concentration of 6  1014 cm3 , and was held at 77 K during the measurements. Figure 2.61 is a plot of the series capacitance C (nF/cm2 ) vs. gate voltage V (volts) at different frequencies ranging from 1 Hz to 4 MHz. Notice that the dielectric constant of the Photox SiO2 layer changes from 7.8 at 1 Hz to only 2.8 at 4 MHz. This brackets the 3.9 value reported for a good SiO2 layer, being higher at low frequencies where there are ionic contributions, and lower at high-frequency because of voids in the layer. Following the analysis method in Sher et al. (1983) an ln GP =! vs. ln ! plot is presented in Fig. 2.62. Once the insulator capacitance is subtracted out the equivalent circuit of the device response is well modeled as a parallel combination of series capacitance/resistance combinations. The impedance is then given by: X

Ci ; 1 C ! 2 i2

(2.81)

X Ci ! i Gp D : ! 1 C ! 2 i2

(2.82)

Cp D

i

and

i

The voltages at which the peaks occur identify the location of states in the band gap and the width the lifetime of those states. The lifetime is related to the effective series resistance Ri of the i th branch through i D Ri Ci . Because the model satisfies the Kramers–Kronig relations all the information resides in either the capacitance Cp or the Gp =! relations. Actually both are used since there are times when it is easier to extract information from one rather than the other. Because of equipment difficulties the data taken between 1 and 10 KHz is less reliable than that in other frequency ranges, so that the results are shown as dotted curves.

2.3 Deep Levels

77

Fig. 2.62 The ln Gp =! curves vs. ! for different gate voltages

The variation of the surface potential with gate voltage is extracted following the Berglund method (Berglund 1966; Sher et al. 1983). From the measured carrier concentration at 77 K, n D 6:2  1014 =cm3 , the intrinsic carrier concentration of ni D 1:15  109 =cm3 , a conduction band effective mass of mc D 0:0182, and a valence band effective mass of mv D 0:55, one gets a Fermi energy EF D 0:226 eV. Adding the surface potential e s yields a surface Fermi energy EFs D 0:181 eV. The flat band voltage for this sample is 0:10 V. Subtracting out the work function difference between Ti and x D 0:3 HgCdTe leaves a surface charge density-induced potential across the insulator capacitance of Qo D 3  109 C=cm2 for a surface density of 2  1010 charges=cm2 . Because the average atom density of this surface is 3:2  1014 atoms=cm2 , this corresponds to one charge every 104 atoms. Figure 2.63 is a plot of the surface density Nss vs. energy E relative to the valence band edge (dot-dashed curve). The total surface density is obtained from the relation Nss D Cp =e where Cp is given by (2.81). The other curves are: 1. A curve extracted from the data that has time constants 1 in the range between 1 Hz and 1 KHz. All these data (dashed curve) all form a sequence of points with continuously varying time constants as shown in Fig. 2.64. They are associated with the valence band tail. 2. A curve extracted from data that exhibits faster responses, between 10 and 100 KHz. These points (connected by a solid line) are associated with the conduction band tail. Their time constant variation is also in Fig. 2.64. 3. The remaining points connected by dotted curves, are the differences between the total curve and the solid and dot-dashed curves. They are localized trap states responses.

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2 Impurities and Defects

Fig. 2.63 Interface densities at 77 K as a function of energy relative to the top of the valence band edge. The curves are (a) the total interface state density curve obtained from Cp at low frequency (dot-dashed curve), (b) valence band tail curve obtained from the Gp =! responses corresponding to the time constant set 1 (dashed curve), (c) the conduction band tail curve corresponding to the time constant set 3 (solid curve), and (d) the difference between the band tail curves and the total capacitance curve corresponding to the localized trap states

Notice that the valence band tail extends further into the gap than the conduction band tail so the usual U-shaped curve in this case has its minimum on the conduction band side of the gap. This is to be expected because the valence band effective mass is large compared to that of the conduction band. The integrated area under the valence band tail from 105 to 185 eV is 3  1011 states=cm2 , which corresponds to only one state every 103 surface atom. The band gap of an x D 0:3 alloy at 77 K is EC D 0:24 eV. The apparent conduction band tail actually extends 0:15 eV above the bulk material’s conduction band edge. This is possible because of the low conduction band effective mass. While the density of states in the conduction band tail rises rapidly below EC , it rises even more rapidly above EC . The set of response times for the valence band states fall on a curve characteristic of a Shockley–Reed center with a cross section of 1:2  1015 cm2 . However the conduction band tail responses do not follow such a curve and must be due to some other mechanism.

2.4 Resonant Defect States

79

Fig. 2.64 The set, f 1 g, of time constant points for the valence band tail state responses, and the set, f 3 g, for the conduction band tail responses

There are nine discrete states visible in Fig. 2.63. The origin of the four state clusters between 0.12 and 0.15 eV is likely due to dangling Te bonds with the other three bonds attached to either three Hg atoms, two Hg and one Cd, one Hg and two Cd, or three Cd. The lowest peak for example has a height of 7  1011 states=eV  cm2 and a half width at half maximum of 5 meV. Thus it has contributing to it 4  109 states=cm2 , or about one state per 105 surface atoms. The peaks are nearly equally spaced with an average spacing of 15 meV. A theory (Casselman et al. 1983) suggests that the spacing between these micro-clusters should be 25 meV in the bulk alloy. Small modifications are to be expected due to the fact that these clusters are at an interface. Since this is a one sample study there is no explanation for the other five discrete states. It would require a multisample investigation in which systematic changes were made to modify the defect structure. The main lesson from this study is that it is an extremely powerful method that deserves to be used more.

2.4 Resonant Defect States Though the usual DLTS can be employed in the study of semiconductor deep level impurities and defects (Polla and Jones 1980b; Jones et al. 1981), it is, however, powerful only to research the energy levels located in the band gap, but not to that of resonant states. In narrow-band semiconductor materials, many levels introduced by the primitive cell potentials of short-range defect centers are located in the valence or conduction band. They are called resonant states because of their interaction with the continuous energy band states. In the past several years, the resonant states in HgCdTe have attracted a lot of attention. For example, a theory of chemical trends

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was presented for sp3 -bonded substitutional deep-trap energy levels in Hg1x Cdx Te materials (x D 0–1) within the framework of the tight binding method (Kobayashi et al. 1982) or more accurately by an LMTO method (Berding et al. 1993). Consideration of the energies introduced by the different charge states of cation substitutional impurity defect states were conducted in Hg1x Cdx Te and detailed results of these energies were given for neutral and single ionization states (Myles 1987). Experimentally, the resonant states in Hg1x Cdx Te can be investigated by transport and optical methods. For example, Ghenim et al. have carried out pressuredependent transport measurements and found a resonant state energy level at 150 meV above the bottom of the conduction band with a concentration in the range of 1:4–7:85  1017 cm3 (Ghenim et al. 1985). Dornhaus et al. have suggested there is a resonant state energy level at 10 meV above the bottom of the conduction band by far infrared spectroscopy and transport techniques (Dornhaus et al. 1975). For some narrow-band semiconductor MIS samples, resonant-state energy levels in the conduction band have also been identified with C –V measurements. For example, a resonant state was found at 45 meV above the bottom of the conduction band in heavily p-type-doped Hg1x Cdx Te (x D 0:21) (Chu 1988; Chu et al. 1992).

2.4.1 Capacitance Spectroscopy of Resonant Defect States The C –V spectroscopy of semiconductor MIS structures can detect the band bending at a semiconductor surface (Sze 1969). Recently, Mosser et al. have found electron quantization features in a surface inversion layer in a C –V study of narrowband semiconductors (Mosser et al. 1988). Due to the potential well caused by surface band bending, the inversion layer electron energy is quantized, with a ground state energy level at E0 , comparable to the band gap Eg . Therefore, no quantized energy level will be filled in the inversion layer until the bending energy reaches Eg , so that the conduction band edge becomes lower than the Fermi energy. However, if the bending energy reaches Eg C E0 so the ground state level is lower than the Fermi energy, the inversion layer states begin to fill. Therefore, the inversion threshold voltage in a C –V curve is delayed, providing the possibility of yielding evidence of the existence of resonant states between the bottom of the conduction band and the ground state level. The Hg vacancy is usually regarded as a shallow acceptor in p-type HgCdTe (Zanio 1978). Its density is especially high in strongly p-type HgCdTe and the opportunity for the vacancies being occupied by impurities is also larger. Theoretical analysis predicts that many impurities located on cation sites form resonant defect states in the conduction band Hg1x Cdx Te samples with x in the range of 0.165–0.22 (Kobayashi et al. 1982; Myles 1987). That compensates the material and reduces Na -Nd . Figure 2.65 illustrates the band bending of a sample with x D 0:21 and Na D 1:87  1017 cm3 , in which Eg D 86 meV is the band gap, E0 D 143 meV is the zero-level energy of the electron subband, ER is a resonant defect state energy level above the bottom of the conduction band, Z0 D 15 nm is the thickness of the inversion layer and Zd D 48 nm is the thickness of the depletion

2.4 Resonant Defect States

81

Fig. 2.65 Band bending of a Hg0:79 Cd0:21 Te.Na  Nd D 1:87  1017 cm3 / sample with a surface electron density of NS D 2  1011 cm2 at 4.2 K

Fig. 2.66 Capacitance as a function of surface potential for HgCdTe MIS samples (Vertical arrows mark proposed energies of several cation substituted impurities)

layer. Figure 2.66 depicts energy positions of several substitutional impurities occupying Hg vacancies according to a rough theoretical estimate of Kobayashi et al. (1982) and another by Myles (1987) in an ideal capacitance spectrum. Obviously, if the band bending makes the resonant energy level lie below the Fermi level, electrons will fill this energy level. If the density of defect states is high enough, this energy level will affect the charging and discharging processes of the surface inversion layer and contribute to the surface capacitance C –V spectrum. In the C –V spectrum of the HgCdTe bulk material fabricated into an MIS structure, an additional peak is observed in the region before the subband threshold voltage. Calculations indicate the existence of a resonant state at 45 meV above the conduction band edge. In the following, a preliminary discussion of the origin of this resonant state is presented. The samples used were slices of a solid state recrystallized, p-type Hg1x Cdx Te with x values of 0:22. They had been mechanically polished and etched in a 1/8% bromine in methanol solution. The MIS structures were produced by first growing 70 nm of anodic oxide in a KOH electrolyte (0.1 N KOH, 90% ethylene glycol, 10% H2 O) with a constant current density of 0:3 mA=cm2 . An 200 nm-thick ZnS layer was then deposited onto the anodic oxide, and finally an Al gate electrode was deposited. This kind of sample structure had a low interface trap state density .<109 cm2 eV1 /, and a small fixed positive charge .<1012 cm2 / (Stahle et al. 1987). Many C –V measurements have been reported on MIS structures of narrow-band semiconductors (Stahle et al. 1987; Beck et al. 1982; Rosback and Harper 1987).

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Using a differential capacitance method, the accuracy can be as high as 0.01 pF/V. The experimental frequency is 233 Hz and the signal UAB is proportional to the difference between the sample and a reference capacitor, C -Cref , as illustrated in Fig. 2.67. At a temperature of 4.2 K, the capacitance of the sample (C ) is the series combination of the sample insulation-layer capacitance .Ci /, and the semiconductor surface-layer capacitance .Cs / (Sze 1969), which can be expressed as: C D

C i CS : C i C CS

(2.83)

Investigated Hg0:79 Ce0:21 Te bulk samples have an effective acceptor concentration of 3–4  1016 cm3 . The capacitance spectra at 4.2 K show an additional peak before inversion occurs for all the samples with NA  1017 cm3 . Figure 2.68 depicts a typical C –V spectrum for a sample taking the anodic oxide and ZnS as dielectric layers, in which Vfb and VT are the flat band voltage and subband threshold voltage, respectively. The regions Vg < Vfb , Vfb < Vg < VT and VT < Vg correspond to accumulation, depletion and inversion regions, respectively. The lower curve in Fig. 2.68 is a surface conductance-voltage spectrum, which exhibits a drastic increase of the surface conductance and surface capacitance at VT , corresponding to the subband threshold voltage. The flat band voltage Vfb is determined by the boundary between the flat part of accumulation region and the steep part of depletion region in the

Fig. 2.67 A schematic of a differential capacitance electrical bridge

Fig. 2.68 A surface capacitance spectrum and a surface conductance spectrum vs. gate voltage for a Hg0:79 Cd0:21 Te sample .NA  1:87  1017 cm3 / at 4.2 K

2.4 Resonant Defect States

83

C –V curve. To determine accurately Vfb , C –V , magneto-resistance oscillation, and cyclotron resonance measurements are required. The VEg in Fig. 2.68 is the energy due to the band bending at which the bottom of the conduction band coincides with the Fermi level. Because there is an additional peak located between the VEg and VT , suggests that a resonant state lies above the conduction band edge. As the energy band bends, electrons will begin to fill in this energy level once the resonant state’s threshold energy level falls below the Fermi level. Given this condition, an increase in the surface capacitance occurs, adding to the contribution from the depletion layer. The effect is equivalent to the addition of an extra surface depletion layer.

2.4.2 Theoretical Model By fitting the capacitance spectrum, the energy level position and the density of resonant states can be deduced. The surface capacitance per unit area of semiconductors is defined as (Sze 1969): CS D

@QS ; @S

(2.84)

where s is the surface potential. Qs is the surface charge density, which can be written as: (2.85) QS D e.NA zd C NR zR C NS /; where zd is the depth of the depletion layer, zR the distance from the resonant state energy level to the Fermi level, that is the resonant level lies energetically above the Fermi level if zR > 0. NA D NA  Nd  NR is the effective acceptor concentration, NR is the density of resonant states, and NS .cm2 / is the electron density in the inversion layer. The surface potential of semiconductor material can be derived from the Poisson equation (Sze 1969): @2   D ; 2 @z ""0

(2.86)

where  is the density of surface charges. Before the subband is filled, the distribution is given by: 8 ˆe.N  C NR /; .0 < z < zR /; ˆ A < (2.87)  D eNA ; .zR < z < zd /; ˆ ˆ :0; .z > z /: d

Assuming that the Fermi level at 4.2 K is pinned to the bulk material acceptor level, the total band bending is then: es D Ef C .Eg  EA /;

(2.88)

where EA is the acceptor level, and Eg is the band-gap energy, whose values can be found from the literature (Scott et al. 1976; Chu et al. 1983; Yuan et al. 1990).

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Ef is the Fermi energy relative to the conduction band edge. The effective acceptor concentration is determined from the slope jKj of that part of the C –V curve corresponding to the depletion layer (Rosback and Harper 1987), and is: NA D

Ci3 ; ""0 eA2 jKj

(2.89)

where A is the area of capacitor. From this relation, the surface capacitance of the depletion layer in the region Vfb 6 Vg 6 VR is given by: s CS D e

1 ""0 NA : 2 Eg  Ea C Ef

(2.90)

And in the region VR 6 Vg 6 VT , the resonant state contributes, and the surface capacitance is: r

""0  .NA C NR / 2 ; CS0 D p  .NA C NR /.Eg  Ea C Ef /  NR .Eg  Ea C ER / e

(2.91)

where ER is the resonant state energy counted from the conduction band edge, and can be deduced from the threshold voltage VR of the resonant peak: ER D

Ci2 .VR  Vf b /2  .Eg  Ea /: 2""0  NA

(2.92)

It is obvious from (2.90) to (2.91) that for VG D VR the band bending makes the resonant state energy ER meet EF , leading to a jump to the surface capacitance, CS D CS0  CS , which is given by: s CS D e

1 ""0 NR  p : 2 Eg  Ea C ER NA

(2.93)

The measured sample capacitance manifests a corresponding change, C D

Ci2 CS ;

.Ci C CS0 / Ci0 C CS

(2.94)

thereby adding a peak to the capacitance spectrum. The density of resonant defect states NR can be derived from C together with (2.93) and (2.94), NR D Cs  ŒNAD  .Eg  EA C ER /1=2 =Œe."s "0 =2/1=2 :

(2.95)

2.4 Resonant Defect States Table 2.8 Energy locations and densities of resonant defect states Insulating Sample layer x NA  .1017 cm3 / 3a SiO2 0.21 1.65 4a A:O: C ZnS 0.21 1.87 5b A:O: C ZnS 0.21 3.17 5b3 A:O: C ZnS 0.21 3.96

85

NR .1017 cm3 / 1.1 0.9 1.8 2.5

ER .eV/ 0.041 0.045 0.047 0.045

The density as well as the energy of resonant defect states can also be calculated by fitting the C –V curve. In Fig. 2.68, the dotted curve is a theoretical fit. From the best-fit one finds that ER D 0:045 eV, and NR D 9  1016 cm3 . Fitted results are listed in Table 2.8 for several Hg1x Cdx Te samples with x D 0:21. The experimental results suggest that for the samples with NA   1017 cm3 an additional peak is always observable, while for the samples with lower NA  , e.g., about 1016 cm3 , no additional peak can be detected.

2.4.3 Resonant States of Cation Substitutional Impurities The origin of this type of resonant state possibly, is the defect state introduced by oxygen occupying a cation site. Theoretical analyses indicates that the energy levels of the neutral and single ionization states of an oxygen atom are located at 50 and 20 meV above the conduction band edge, respectively, for a Hg0:79 Cd0:21 Te alloy (Kobayashi et al. 1982). This result is similar to the C  V experimental value. The possibility of oxygen atoms occupying cation sites can be estimated qualitatively. If the sample is exposed to air after annealing or etching, or in the process of anodic oxidation, oxygen atoms may occupy cation sites. This can lead to pollution of the bulk material. In the standard Br–alcohol chemical etching process, the surface damage is normally as deep as several tens of nanometers, and an activated Te-rich layer at the surface is easily oxidized. Then oxygen atoms easily diffuse into the bulk via a Hg vacancy assisted mechanism (Herman and Pessa 1985). In the anodic oxidation process, the surface oxygen concentration is about 50% (Stahle et al. 1987), thus a large number of oxygen atoms are present and combine with Hg, Te, and Cd to produce the oxidized films. In this process, it is inevitable that some of the Hg vacancies will be occupied by oxygen atoms. It has been determined experimentally that the process of the replacement of Hg vacancies with impurity atoms will not go on without limit, and saturates at a probability, . Thus impurity atoms can only replace a part of the Hg vacancies. If the total Hg vacancy density is NA , the number of Hg vacancies being replaced by impurities, NR , is then NA when the system reaches an equilibrium state. It was deduced from the fitted results of several samples that  for oxygen is about 0.3–0.4. According to this analysis, it is understandable why only for samples with high initial Hg vacancy densities, is the additional peak observed. The absolute value of the density of oxygen atoms replacing Hg vacancies in low initial density samples

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is low. While even for initially low Hg vacancy densities a jump of the surface capacitance can be introduced, it is clear from (2.93) that: p  NA : C / p 1

(2.96)

This means for samples with low NA , the jump in the capacitance is small and is likely to be masked by interfacial and inhomogeneous effects. An additional reason is that the threshold energy E0 (near ER / of the ground subband state is smaller for a sample with identical composition but lower NA . This indicates that the inversion threshold voltage VT is close to VR and the capacitance jump in inversion due to a resonant state makes only a minor contribution that may not be detectable. To investigate the mechanism further, the change of the defect state densities induced by annealing is studied along with the impact of an Au doping treatment. If the defect states are due to oxygen atoms occupying Hg vacancies, in a lowtemperature, Hg saturated annealing process the vacancies will be filled with Hg atoms and the oxygen atoms will be driven out. Hence the density of resonant states will decrease. On the other hand, if the p-type acceptor initially in the sample is not a Hg vacancy but Au, the resonant state will not be detectable even if the initial acceptor concentration is very high. If a sample, in which initially the resonant state peak is obviously observed, is then exposed to a Hg saturated low-temperature anneal to reduce the impurity density and its C –V curve is measure again. According to this model the resonant peak should be reduced. The sample is then doped with

Fig. 2.69 Capacitance spectra of a Hg0:79 Cd0:21 Te sample .NA  1:65  1017 cm3 / before and after annealing, and after an Au doping process

2.5 Photoluminescence Spectroscopy of Impurities and Defects

87

Au to make it an initially high p-type density sample again and the C –V measurement is repeated. The results are depicted in Fig. 2.69. The top spectrum is that of a HgCdTe=SiO2 dielectric film sample (NA  D 1:65  1017 cm2 /, which clearly shows the resonant state peak. A theoretical fit indicates the density of resonant states is 1:1  1017 cm3 and ER is 0:041 eV. The middle spectrum is that of the same sample after a 10 h anneal at a temperature of 250ı C. The acceptor concentration is 5:9  1016 cm3 and the resonant state peak gets weaker. A theoretical fit suggests that the density of the ER D 0:041 eV resonant state reduces to 4  1016 cm3 . The bottom spectrum represents the result after Au doping and 10 h anneal at a temperature of 250ı C. Following this process, the low-density sample becomes a high-density one, 6:95  1017 . However, no obvious resonant state peak appears. A theoretical fit indicates that the resonant state density is still 4  1016 cm3 . This illustrates that the resonant state does not depend on the acceptor concentration but on the Hg vacancy concentration. It therefore suggests that this resonant state originates from oxygen atoms replacing Hg vacancies and that annealing can reduce or eliminate its influence.

2.5 Photoluminescence Spectroscopy of Impurities and Defects 2.5.1 Introduction The optical techniques that can be used to explore the nature of impurities and defects are generally comprised of PL spectroscopy, infrared transmission/reflection spectroscopy, magneto-optical spectroscopy, and PTIS, among which the PL spectroscopy is deemed to be an important and fundamental one. PL spectra from semiconductors offer information about not only intrinsic optical processes, but also impurities and defects. In fact, it has been advanced to be a standard technique for the study of semiconductor material properties (G¨obel 1982). A PL measurement generally requires almost neither special sample preparation nor complicated instrumentation, and most importantly, it is nondestructive. It therefore attracted wide attention in the last few decades, and as a consequence, a huge related literature was published in journals and conferences in the field of semiconductors and low-dimensional systems. For wide bandgap semiconductors, PL spectroscopy is usually a valuable tool for monitoring the quality of material growth, evaluating the properties of heterojunction structures, and estimating indirectly the density of minority carriers and defects so as to predict device performance. However, PL study of narrow-gap semiconductors was seldom performed, mostly due to the following reasons: 1. A PL signal decreases dramatically with the energy gap, due to the enhancement of the nonradiative Auger recombination process. 2. At room-temperature environmental thermal emission in the mid-infrared spectral region is about 200 times stronger than the general PL signal.

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3. The solid state detects available for PL spectroscopy studies require a much higher detectivity than photomultiplier tubes (PMT); and in the mid- and farinfrared spectral regions, no PMT is available. 4. Disturbances from the absorption of atmospheric and optical materials is serious in the mid- and far-infrared regions. Thanks to the revolutionary progress made in computer science and technology, Fourier transform infrared (FTIR) spectrometer-based PL techniques have been developed. This significantly enhances the sensitivity and the spectral resolution and therefore dominates the study of the PL processes in semiconductors in the near- to mid-infrared. To extend the measurable spectral range to mid- and even far-infrared, suppression of the environmental thermal emission became crucial. This gave birth to the so-called DM-PL technique. Depending on the particular choice of the “modulation,” the DM-PL technique may yield a measurement in the mid- and far-infrared regions with a reasonable SNR and spectral resolution. This makes DM a distinguishable technique relative to conventional PL measurements. Since the first PL data for HgCdTe was reported by Elliott et al. (1972) in 1972, quite a lot HgCdTe samples with different Cd concentrations from 0.197 to 1 (CdTe) have been characterized. However, apparent inconsistencies exist among the data as well as its explanations, which most probably, stem from the following facts: (1) the samples used by different authors’ groups were prepared by different methods and hence were of different quality and (2) the inaccuracy of energy gap determinations of HgCdTe is of the order of a few milielectron volts, which is the same order as the exciton binding energies, making the uncertainty of the PL signal identification even worse. It was expected that a systematic PL spectroscopic study could be performed by three different approaches (Tang et al. 1995): (1) starting from the high Cd concentration end (2) in the mid concentration limit near x D 0:4, or (3) at the low concentration end near the range where IR applications are prevalent. At higher concentrations standard PL techniques are adequate, but as the concentration is lowered it is necessary to go to DM-PL methods. Generally, the PL signal from a high quality Hg1x Cdx Te sample with Cd concentrations in the range of 1.0–0.7 are dominated by (1) nearly free but still localized exciton transitions, (2) a bound localized exciton, and (3) phonon replicas of localized or bound excitons. Meanwhile, the PL signal from Hg1x Cdx Te samples with a Cd concentration less than 0.26 appears usually as only a simple single peak. Due to the small binding energy of a nearly free exciton and the transition oscillator strength of low Cd concentration Hg1x Cdx Te, it is usually difficult to distinguish whether a peak is from a band-to-band transition or due to a free exciton. Furthermore, the difference between the spectral line shapes of these two transition mechanisms is so small, that a lineshape fitting process for the PL spectrum may not work well (Tomm et al. 1990). Considering the exciton binding energy is very small in low Cd concentration HgCdTe samples, as well as the weak Hg–Te bond that enables the formation of defects and may introduce disorder fields to dissociate the excitons, the PL peak at 4.2 K is quite possibly caused by a band-to-band transition. The localization of excitons result from the alloy disorder-induced fluctuations of potential

2.5 Photoluminescence Spectroscopy of Impurities and Defects

89

fields whose energy has been experimentally determined using thermally assisted dissociation experiments to follow a x.1  x/ behavior. When x is around 0.5, the energy takes on its maximum value which is as large as 10 meV.

2.5.2 Theoretical Background for Photoluminescence In 1990, Tomm et al. (1990) reviewed systematically infrared PL in narrow-gap semiconductors. In this section, the theoretical background will be briefly introduced to further the understanding of the forthcoming materials. The process of PL can be simply described as follows; when a light beam with intensity I0 and photon energy „! > Eg impinges on the surface of a semiconductor with a band gap of Eg , it penetrates into the sample and will be absorbed with an absorption coefficient ˛ far some distance below the surface. If the reflection and/or scattering at the interface are ignored, the intensity is then reduced to Ix D I0 exp.˛x/. The absorption of these photons leads to a nonequilibrium carrier generation process. In general, these photon-generated nonequilibrium carriers will relax rapidly to the extremes of the conduction and valence bands, respectively, so as to reach a minimum energy. This energy configuration can be described by a quasi-equilibrium Fermi level distribution. The effective temperatures of electrons and holes are normally higher than the measured sample temperature due to a heating effect. The process of carrier generation is faster than that of diffusion. Thus, the distribution of the photon-generated nonequilibrium carriers is nonuniform, which leads to the existence of diffusion to reduce the concentration gradients. There are several recombination mechanisms inside the semiconductors and at surfaces. For a constant excitation power, the nonequilibrium carriers will form a quasistatic spatial distribution. In the case of a weak excitation, the lifetime of these nonequilibrium carriers is basically independent of their concentration. If the recombination of these carriers is realized by radiative recombination, the accompanying photon emission is the PL process. The PL internal process results from three different but interconnected processes: light absorption causing nonequilibrium carriers generation; diffusion of these carriers and radiative recombination of resulting electron–hole pairs; and the propagation of the radiative recombination induced photons in the sample and its subsequent emission from the sample (Shen 1992). Because the PL process is due to a recombination process, it is necessary to examine the different recombination process in HgCdTe materials. It is known that there are both radiative and nonradiative recombination processes in narrow gap semiconductors. Surfaces influence the whole recombination process. However, the surface can be carefully treated before a PL measurement so its influence is reduced significantly to a point where it can be ignored. When the PL processes in HgCdTe are analyzed, the features of narrow gap semiconductors must be taken into account. The dielectric constant is large and the electron effective mass is small, resulting in a very weak exciton binding energy. For example, for Eg D 100 meV gap, the binding

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2 Impurities and Defects

energy of a free exciton is only about 0.3 meV. (For the same reason a hydrogenic donor impurity is shallow in HgCdTe.) Another remarkable feature of narrow gap HgCdTe is the intensity of the Auger recombination process, which is an important nonradiative process (Petersen 1970; Kinch et al. 1973; Pratt et al. 1983), and gets stronger with a decrease of the band gap. The relation between the recombination rate RA and Eg is given by: RA  Egˇ ; (2.97) where ˇ takes on a value between 3 and 5.5 (Ziep et al. 1980). For n-type semiconductors, the energy released in an Auger-1 process, one in which the recombination of an electron in the conduction band and a hole in the valance band, is transferred to another electron so that its energy is increased to conserve energy and momentum in the overall process. The lifetime of this Auger recombination in n-type HgCdTe can be written as (Lopes et al. 1993):

A1 D i

A1

D

i 2n2i A1

.n0 C p0 /n0 1 3:8  1018 "21 .1 C / 2 .1 C 2/ exp



.1 C 2/Eg .1 C /kB T



m0 kB T jF1 F2 j me Eg

3 2

; (2.98)

where ni is the intrinsic electron concentration, n0 and p0 the thermal equilibrium concentrations of electrons and holes, respectively,  is the ratio of the effective masses of an electron and a hole, "1 the high-frequency dielectric constant, Eg the band gap, kB the Boltzmann constant, and T is the temperature. jF1 F2 j are overlap integrals of Bloch wave functions, F1 between the conduction and valance bands, and F2 between the conduction band edge and an excited conduction band state. The product when fit to experiment is taken to have a value is in the range of 0.1–0.3. However, in a recent paper where good band structures are calculated, it has been shown that the product is not well approximated by a constant but depends on the momentum k, the alloy concentration, and the temperature (Krishnamurthy 2006). For p-type HgCdTe samples, just considering an Auger-1 process is not sufficient, an Auger-7 process is also important (Lopes et al. 1993; Petersen 1983). An Auger-7 process is one in which the recombination energy and momentum of an electron in the conduction band and a heavy hole is taken up by the excitation of an electron from the light hole subband to the heavy hole subband. The corresponding lifetime is given by (Lopes et al. 1993):

A7 D

i 2n2i A7 : .n0 C p0 /p0

(2.99)

i i Casselman (1981) calculated the ratio  of A7 and A1 , which is a function of temperature and alloy concentration. For HgCdTe with a concentration x in the range 0.16–0.3, at temperatures in the range 50–300 K, the value of  lies between 0.5 and 6. Specifically, for x D 0:22 and 0.3,  is independent of temperature and

2.5 Photoluminescence Spectroscopy of Impurities and Defects

91

has a value of about 1.5 and 0.5, respectively. Combining these two mechanisms together, the total Auger lifetime A of p-type HgCdTe is given by (Lopes et al. 1993):

A1 A7 : (2.100)

A D

A1 C A7 Similar to the recombination processes in wide gap semiconductors, the Schockly– Read process also exists in the nonequilibrium carrier recombination of narrow gap semiconductors. It too is a type of nonradiative recombination. In this kind of recombination process, nonequilibrium carriers recombine through a pathway provided by deep impurity states and/or dislocations providing energy steps to enhance the recombination probability. If the density of Shockley–Read centers is much lower than the carrier concentration, the Shockley–Read recombination lifetime SR is determined by (Lopes et al. 1993):

SR D

.n0 C n1 / p0 C .p0 C p1 / n0 .n0 C p0 /

(2.101)

with  ET  EC kB T   EV  E T p1 D NV exp ; kB T 

n1 D NC exp

(2.102)

p0 D .vp p Nt /1

n0 D .vn n Nt /1 where n and p are the capture cross sections of electrons and holes, and n and p are their thermal velocities, respectively. ET is the trap energy. According to the calculation by Schacham and Finkman (1985), the inter-band radiative recombination e lifetime is given by:

r D

1 ; B.n C p/

(2.103)

where 13 p



m0 me C mh

 32



m0 m0 "1  1C  C  B D 5:8  10 me mh h i 3  .300=T / 2 Eg2 C 3kB TEg C 3:75.kB T /2

 ; (2.104)

and where "1 is the high-frequency dielectric constant, me and mh electron and hole effective masses, m0 the mass of free electron, and kB is the Boltzmann constant.

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For the nonequilibrium carriers in narrow gap HgCdTe, there are three main recombination mechanisms: radiative, Shockley–Read, and Auger recombination. These recombination mechanisms determine the lifetime of the nonequilibrium carriers. In the case of low injection, the relation between the corresponding lifetimes ( R ; A , and SR ) and the lifetime of a nonequilibrium carrier in a material is: 1 1 1 1 C C : D

A

R

SR

(2.105)

For a given density of nonequilibrium carriers in HgCdTe, the recombination can be realized by a radiative recombination process or an Auger and/or Shockley–Read nonradiative recombination processes. The radiation efficiency is the probability of a photon emission in a radiative recombination, which is given by 

1 1= R D

R : R 1= 1C C

A

SR

(2.106)

Therefore when the excitation power is constant, the PL signal strength is determined by internal recombination mechanisms, and the corresponding PL spectrum depends on a competition between internal radiative recombination and the other nonradiative recombination processes. To enhance the PL signal intensity and improve the SNR, it is necessary to suppress the probability of nonradiative recombination. Now let us consider the major PL processes occurring near the band-edge of HgCdTe. As is well known, HgCdTe has a zincblende cubic structure. The extremes of the valence- and conduction-bands are in the center of the first Brillouin zone, and it is therefore a direct-gap semiconductor. The optical properties, especially the PL near the band edge, are mostly determined by the band edge structure. For a direct-gap semiconductor, nonequilibrium carriers at the band edge can recombine through 1. 2. 3. 4.

An inter-band transition (intrinsic transitions) Free-exciton recombination Bound exciton recombination Radiative recombination of a free electron and a neutral acceptor .eA0 / or a free hole and a neutral donor .hD 0 / 5. A donor–acceptor pair combination.

For narrow-gap HgCdTe, possibility number 3 is the main contributor through combinations of donor-bound exciton (D 0 X ) and acceptor-bound exciton .A0 X / processes. These recombination processes are illustrated in Fig. 2.70. However, not all the radiative recombination processes in Fig. 2.70 will be observed for a given set of circumstances. Under a similar excitation condition, the PL spectra change with a sample’s temperature. For example, at high-temperature, the direct band-to-band transition is always observable. But it is weak, even difficult to detect, at low-temperature. In the latter case the recombination through an

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Fig. 2.70 Radiative recombination mechanisms of nonequilibrium carriers near the band edge of HgCdTe. (a) direct band-to-band transitions, (b) free-exciton recombination (FE), (c) donor-bound exciton recombination .D 0 X/, (d) acceptor-bound exciton recombination .A0 X/, (e) donor– acceptor pair recombination .D 0 A0 /, (f) free electron–neutral acceptor recombination .eA0 /, and (g) free hole–neutral donor recombination .hD 0 /

exciton or impurity generally dominates because impurity and exciton states have large populations at low-temperature. The impurity assisted PL obviously changes drastically with the type and density of impurities. The PL spectrum also depends on the experimental conditions, such as excitation power. These conditions therefore provide a criterion for clarifying the mechanisms responsible for different PL peaks (Schmidt et al. 1992a, b). As mentioned before, the light emission process is related to the light absorption process. For the PL process in the case of equilibrium and quasiequilibrium, the generation rate of photoelectron/hole pairs is equal to their recombination rate, which is known as von-Roosbr¨ock–Shockley relation. It can be written as: Rsp .„!/ D ven  G.„!/  ˛ .„!/ 

nu n0l ; nl n0u  nu n0l

(2.107)

where Rsp is the spontaneous emission transition rate per unit volume in the energy space element d .„!/ at „!, en the propagation velocity of energy, nl the occupation probability of the lower state, n0l the probability that the lower state is empty, nu the occupation probability of the upper state, n0u the probability that the upper state is empty, ˛.„!/ the absorption coefficient, G.„!/ the density of the radiation field in the energy space element d.„!/ at „!. This relation can be simplified for a direct-gap transition using parabolic energy bands:   p 1 „!  Eg  EFn  EF .„!/2  ˛.„!/  exp ; Rsp .„!/ D .c/2 „3 kB T

(2.108)

where  is the refractive index, EFN and EFP are the quasi-Fermi levels of electrons and holes, respectively, Eg is the band gap.

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Because PL is a process involving generation and recombination of nonequilibrium carriers, the quasi-equilibrium distribution of carriers described by quasi-Fermi levels is appropriate. In principle, the radiative recombination rate and line shape of the emission spectrum can be derived from the corresponding absorption spectrum taken for the same sample with a given refractive index . This is important when an experimental PL spectrum is to be understood, such as the emission spectral band width in bulk GaAs (Griffiths and Haseth 1986). For the band-to-band PL transition in HgCdTe at high-temperature, a similar method can be employed to characterize the PL peaks. For a PL study of narrow-gap HgCdTe semiconductors in the infrared region, a FTIR spectrometer is an obvious choice. The FTIR spectroscopic technique has been developed to such a level that it not only provides the two advantages of through-put and multi-channels, but also may enable the possibility of incorporating a modulation process into the PL measurement. The FTIR spectrometer makes use of the relation between an interferogram of a Michelson interferometer and an optical spectrum. The spectrum is deduced by first recording the interferogram, and then Fourier transforming it to obtain the final spectrum. In the following, the basic principle employed is described (Griffiths and Haseth 1986; Fuchs et al. 1989). Considering a case in which a monochromatic light beam, with amplitude a and wavenumber , passes through a beam splitter, the reflection coefficient is denoted by r and the transmission coefficient by t . The beam splitter splits the light into two parts: one is a reflected beam with amplitude ra and transmitted beam with amplitude ta. The transmitted beam goes to the fixed mirror M1 of the interferometer, and the reflected beam goes to the moving mirror M2. Then the beams are reflected back to the beam splitter and recombined. The motion of the moving mirror changes the total path length of the reflected beam, and the optical path difference between the two beams results in temporal constructive and destructive interference. The jointed beam is collected by a detector. The signal amplitude collected by the detector is: AD D r  a  t .1 C e i' /:

(2.109)

The intensity of this signal is: ID .x; / D AD AD D 2RTB0 . /.1 C cos '/;

(2.110)

where R, T are the reflectance ratio and transmittance ratio of the beam splitter, B0 ./ D aa is the intensity of the incident beam, x is the optical path difference, and ' is the phase difference between the two beams from the fixed and moving mirrors. x ' D 2 D 2 x; (2.111)  When the incident beam has a random spectral distribution, ID .x; / D dID .x/=d is an integral with the spectral element of an infinitely narrow line width d : Z

1

2RTB0 . / Œ1 C cos.2 x/ d :

ID .x/ D 0

(2.112)

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The final spectrum, B , can be obtained by doing a Fourier transformation of the interferogram: Z 1 ID .x/ei2x dx: (2.113) B D 1

Therefore, for any wave number, the spectral density B can be obtained from the Fourier transform after the interferogram is known. However, the above method is difficult to exercise in practice. In fact, the sampling points are limited and the arm length of the Michelson interferometer in the FTIR spectrometer is finite. The limitation this imposes on sampling points and the sampling range results in side lobe oscillations. These can be suppressed, nevertheless, by an apodictic treatment. That is, the Fourier transformation is performed on the resultant interferogram after having been multiplied by an apodictic function. The Happ–Genzel function and the Boxcar function are both common apodictic functions in the Fourier transformation of a spectrum. The suppression by the apodictic treatment may, in addition, result in a line broadening and degradation of the spectral resolution. Thus a compromise has to be made between the spectrum distortion and the reduction of the resolution. The Happ–Genzel function can effectively suppress the side lobes and at the same time not decrease the resolution so remarkably. Thus it is frequently used, and is especially useful for high-resolution spectrum measurements. In an ideal experiment, the system noise arises from the infrared detector. To reduce the noise, the noise component outside the measured spectral range is always eliminated by a suitable electrical filter. However, the electrical filter introduces an additive phase shift to the signal. The optical path, data acquisition and other electronic circuits may also introduce additive phase shifts (Griffiths and Haseth 1986). Thus, it is necessary to use a phase correction to eliminate these additive phase shifts. The spectrum after phase correction can be written as: Z

1

A.x; "/ID .x C "/ cos 2 .x C "/;

B. / D

(2.114)

0

where A.x; "/ is an apodictic function. Thanks to the development and application of the algorithm for fast Fourier transformation (FFT), the rapid-scan mode of a modern FTIR spectrometer ensures a spectrum will be obtained in just several seconds or minutes with high resolution and SNR. Briefly, the major advantages of the FTIR spectrometer are as follows (Griffiths and Haseth 1986): 1. Multi-channel advantage. By using this interference method, the spectral signals from all the frequencies can be obtained in a single scan of the moving mirror. Thus the measuring time can be significantly reduced with a similar SNR and resolution. In contrast to the

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conventional dispersive technique, a spectrum with significantly enhanced SNR can be recorded for a given measuring time. For the dispersive technique, on the other hand, the intensity of a received signal with wavenumber l , is given by: Z

tCT

B0 . l /dt D B0 . l /T;

(2.115)

t

where v is the velocity of the moving mirror. For a spectral element with wavenumber 1 , the FTIR technique uses cos.2vl x/ D cos Œ2vl . t / to encode it. Then N spectral elements are coded and their signals are observed simultaneously in time T (N elements in time T ). Thus the intensity of the received signal for a given spectral FTIR element is given by: Z tDNT B0 . i /dt D N ŒB0 . l /T  : (2.116) 0

It is obvious that the signal intensity increases by apfactor of N using this FTIR technique and thus the SNR increases by a factor of N !. 2. High throughput advantage. In contrast to the slit of dispersive spectrometers, all the radiative power from the light source passing through the aperture is received by the detector of the FTIR spectrometer. Thus its throughput is improved many times relative to that of dispersive spectrometers. Another obvious advantage of the FTIR technique is its spectral resolution, which is determined by the arm length of the Michelson interferometer from the mirrors to the beam splitter. Therefore, the energy resolution is identical over the whole spectral range being measured and is easy to upgrade. The disadvantage of the FTIR technique, if there is any, is its relatively high price and because it obtains a spectrum indirectly. The spectrum may be distorted if any factor in the data acquisition and/or processing is not implemented carefully. The preferred excitation source for a PL measurement is the 514.5 or 488.0 nm spectral line of an ArC laser, even in the measurement of narrow-gap semiconductors. A HgCdTe sample to be studied is mounted on the cold finger of an optical Dewar to reach low enough temperatures for the measurements, where weak radiative recombination processes exist in these narrow-gap systems. The sample is usually immersed in liquid Helium or a Helium gas during the measurement. To control and determine the sample’s temperature accurately, a sensor and a heater are installed just above the sample. The accuracy of the temperature can be controlled within ˙0:1 K, so that a study of temperature effects is reliable in a range of temperatures from 4 to 77 K. The PL signals are collected by a parabolic mirror and sent to an FTIR spectrometer to record the spectrum. The choice of detectors depends on the spectral region of the PL measurement. Liquid-nitrogen cooled InSb and HgCdTe detectors are commonly used. At times Hg1x Cdx Te with a large x, InAs, or Ge detectors can also be a proper choice. The matching of the spectral region to the detector of the FTIR is important to ensure a good measurement.

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Fig. 2.71 Environmental thermal emission in a conventional PL measurement (with a liquid-nitrogen cooled HgCdTe detector and a KBr bean splitter)

To realize PL measurements in the mid- and far-infrared spectral regions, it is crucial to advance the conventional FTIR PL technique to the DM-PL method. In fact, even in the 4–5 m spectral region, PL spectra measurements are already very difficult due to strong environmental background thermal emission, which is illustrated in Fig. 2.71. This noise is generally at least 200 times stronger than the PL signal. The double-modulated PL (DM-PL) technique eliminates the influence of the environmental thermal background, and is thus important for the nondestructive detection and evaluation of materials working in these regions. To eliminate the influence of the background thermal emission, the main possible improvements to the conventional FTIR PL technique are as follows: Frame subtraction method After a normal PL measurement, the background spectrum is measured. Then the background is subtracted from the PL spectrum. It is a convenient method requiring no hardware modification, and is effective for samples with strong PL signals that are larger than, or at least of the same order of magnitude as the background signals. However, for most samples the PL signal is not strong enough to ensure such a treatment will be effective. A more efficient technique is thus called for. Phase sensitive excitation (PSE) technique The realization and application of this method to HgCdTe PL measurement was first developed by Fuchs et al. (1989), Fuchs and Koidl (1991). The technique is illustrated in Fig. 2.72. According to the principles behind the FTIR technique, the inter-ferogram of the detected light passed by a Michelson interferometer, can be written: I.x/ D

1 X 1X Ii C m Ii cos.2 i x/; 2 2 i

(2.117)

i

where i is the wavenumber, Ii is the density of the monochromatic light at this wavenumber, x.t / D t is the optical path difference of the interferometer, and m is the modulation efficiency. For an ideal interferometer, m is taken as 1.  IPL D IPL0

 1 1 C cos.f0 t C 1 / ; 2 2

(2.118)

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Fig. 2.72 Schematic of a phase sensitive excitation (PSE) Fourier transform infrared (FTIR) spectrometer-based PL technique

where IPL0 is the output power of a CW laser, 1 is the generated phase difference in this process, f0 is given by the alignment the He–Ne laser incident on the FTIR, and is given by: (2.119) f0 D 2 0 : According to Fuchs et al., the PL signal is proportional to the power density of the excitation laser, Ii .t / D CIPL .t /, then  Ii .t / D Ii Thus we find: Ii .x/ D

 1 1 C cos.f0 t C / : 2 2

  1 1 1 Ii .2  m/ C cos.f0 t C / 2 2 2   1 1 1 C cos.f0 t C / cos.2 i x1 /: C Ii m 2 2 2

(2.120)

(2.121)

By making a transformation, the appropriate difference equation becomes:   1 1 1 1 C cos.f0 t C / C Ii m  Ii .x/ D Ii .2  m/ 2 2 2 2  1 1 1 cos.2 0 t C/C cosŒ2. 0 C i /t CC cosŒ2. 0  i /t C :  2 4 4 (2.122) The modulated PL signals transfer 50% of the intensity into each of the two side band of the modulation frequency f0 . For a commercial FTIR spectrometer, an He– Ne laser is used as the alignment laser, and hence f0 is approximately 15;798 cm1 . The resulting modulated PL signals are therefore kept away from the region of the background thermal emission and a PL spectrum of relatively high quality

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is attained. The problem is, however, that the assumption, Ii .t / D CIPL .t /, is not always correct. For the spectral region of narrow gap semiconductors, the possible recombination mechanisms for nonequilibrium photogenerated carriers consist of band-to-band transition; bound-to-free recombination; donor-bound exciton recombination (D 0 X ) and acceptor-bound exciton recombination (A0 X ); free-exciton recombination (FE); and donor–acceptor pair recombination (D 0 A0 ). Among these mechanisms, only the PL between FE and bound excitons strictly fulfills this assumption (Schmidt et al. 1992a, b). As a result, this technique may lead to a distortion of the spectrum. Simulation results also support this contention. Phase sensitive detection (PSD), or namely, DM-PL technique DM-PL spectroscopy was first proposed by Griffiths and Haseth (1986), followed by Reisinger et al. (1989). The thought behind this method is as follows. Besides the modulation introduced by the Michelson interferometer in an FTIR spectrometer, an additional modulation with higher frequency is applied to the CW laser by, for example, a mechanical chopper. This chopped light is sent into the sample and then into the FTIR and the signal is detected with a lock-in-amplifier (LIA) referenced to the chopper frequency. The demodulated light is then passed through a preamplifier, the inverse Fourier transform unit and a filter. The final spectrum is then obtained (Chang 1995). For a high quality spectrum the modulation frequency of the excitation laser light should be much higher than the highest frequency component of the interferogram and its period must be at the same time much smaller than the integration time constant of the LIA. This integration time is limited by the sampling frequency of the FTIR. The integration time should be slightly less than or equal to the sampling cycle time in order to obtain a SNR as large as possible. Formerly the DM-PL technique was limited by the chopper frequency. To mitigate this problem the scanning speed could be decreased. On the other hand, a low scanning frequency would decrease the SNR. A better solution is to increase the modulated frequency. Chang (1995) increased the modulation frequency by using an acousto-optic modulator (AOM) and in so doing the quality of the PL spectrum was greatly improved. The experimental setup for the DM-PL spectroscopy is illustrated in Fig. 2.73. The light from the CW laser irradiates the AOM at the Bragg angle. The first-order

Fig. 2.73 An experimental setup schematic for a DM-PL measurement

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diffraction beam is used as an output, and now due to the modulation of the AOM it is a “square wave” with a frequency of 100 KHz. It then impinges onto the sample in a Dewar and the PL signal from the sample with the AOM modulation frequency is collected by a parabolic mirror and fed into the entrance of the FTIR spectrometer. After passing through the Michelson interferometer of the FTIR spectrometer, the PL signal is focused onto an infrared detector, the output of which is fed to an LIA. Meanwhile, the modulation frequency of the AOM is applied to the LIA as its reference. The output signal of the LIA is fed back into an amplifier, a filter, and an inverse Fourier transformation unit. In this way, only the PL signals at the modulation frequency and at a fixed phase difference relative to the modulated excitation laser light is detected and amplified, and the background thermal emission is totally suppressed. A PL spectrum is thereby obtained, free of the background thermal emission disturbance. To ensure a successful PL measurement with the DM-PL technique, particular problems should be treated with great care: a. The choice of the AOM frequency. Theoretically, the increase of the modulation frequency is helpful for improving the SNR of the spectrum in the case of the LIA working at a particular integration time constant. However, the increase of the frequency will result in a decrease of the directivity D  due to a limited response time of the detector. Figure 2.74 shows the D  as a function of frequency for a photovoltaic HgCdTe detector and a TGS (TGS: triglycine sulfate detector operated at room temperature) detector, respectively. It is clear that the TGS detector cannot be used for this purpose due to its slow response. The response time of a photovoltaic HgCdTe detector is fast and hence is the best choice in this case. Nevertheless, for an FTIR spectrometer equipped with a photoconductive HgCdTe detector whose response time is a bit longer, it is experimentally shown that a quite nice SNR may be ensured if the modulation frequency is taken to be no higher than 100 KHz.

Fig. 2.74 Detectivities D  as a function of frequency for HgCdTe and TGS detectors, respectively

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b. The choice of the cutoff frequency of the band-pass filter. A monochromatic beam with wavenumber  corresponds to a sinusoidal interferogram with a Fourier frequency 2 v after being modulated by the Michelson interferometer. Given the velocity of the moving mirror, the sinusoidal wave frequencies can be calculated for monochromatic beams with different wave numbers in this way. In a real PL measurement, the spectral signal only shows up in a certain region. Thus the interferogram can be filtered with an electrical band-pass filter so as to let only the useful signal within the spectral range pass through. The SNR in this manner is improved. c. The choice of a suitable phase correction. To eliminate the additive phase shifts, a phase correction is applied in the optical measurement to the FTIR spectrometer (Griffiths and Haseth 1986). In general, an autocorrection method is used. Data points around the zero path-difference point (a typical value is 256) are chosen for the transformation. For a conventional optical spectrum measurement, these sampling points are strong enough to produce a good SNR. The array  can be written: (2.123)  D arctan.Imi =Rei /; where i labels the points, Im and Re refer to the imaginary and the real part of transforms, respectively. In general,  is basically thought of as removing the noise in the real phase array of the spectrum. However, it is not appropriate for a PL measurement using DM-PL spectroscopy due to the weak signal and large noise. On one hand, they lead to errors in the choice of the zero path point. On other hand, even for points around the zero path point, their SNR is not high and results in large error in the phase array calculation. The wrong choice of the zero path point directly causes a large distortion of signals. Thus, this type of autocorrection method is not suitable in a PL measurement of HgCdTe. One solution is to choose the zero path point manually and perform a phase correction. Another solution is to make use of background in high- and low-pass filtering conditions and perform a phase correction from a calculation. According to a brief comparison (Shao et al. 2006), the double modulation was superior to a frame-to-frame subtraction, though the former experienced a rather tough limitation on the choice of the sampling time constant of the LIA for shortwavelength PL measurements. The PSE modulation PL method, on the other hand, relaxes the restriction on the sampling time constant of the LIA. While it separated the PL from the background thermal emission, the dynamic range of the detector, and hence the SNR of the PL signal as well, were limited. Also it can suffer from interference with the intense line at the carrier frequency and could not be run safely with high spectral resolution. Furthermore, both the PSD and PSE modulation techniques were based on a continuous-scan (also known as a rapid-scan) FTIR spectrometer, and can not be used to eliminate the disturbance of the internal He–Ne laser line for the PL spectra around 630 nm, because of either a difficulty of realization or the presence of the He–Ne laser line as an intrinsic characteristic. For this reason, and especially to significantly improve the SNR and reduce time cost of a single measurement, Shao et al. designed and demonstrated a new type of DM-PL based on a modern FTIR spectrometer with a step-scan operational mode (Shao et al. 2006).

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Step-scan FTIR spectrometer-based modulated PL technique The experimental setup for a step-scan FTIR spectrometer-based modulated PL technique is similar to the previous DM-PL one, except for the fact that (1) the FTIR spectrometer runs in step-scan mode, in which during each step the laser is amplitude-modulated a process that fully relaxes the limitation on the choice of the modulation frequency without any trade off, (2) a combination of a mechanical chopper and an LIA is used to replace the combination of an AOM and an LIA, and (3) the pumping laser is amplitude-modulated by a mechanical chopper whose frequency serves an a reference for the LIA. A typical result established for a narrow-gap HgCdTe sample is depicted in Fig. 2.75 together with a representative PL spectrum obtained by Chang (1995) using a continuous-scan DM-PL technique. The significantly improved SNR of the

Fig. 2.75 Comparison of PL spectra taken by: (a) a continuous-scan FTIR DM-PL, and (b) a newly developed step-scan FTIR modulated PL technique. The upper PL spectrum (a) was measured at a temperature of 4.2 K, while the others (b) were taken at either 77 K or room temperature

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PL spectrum recorded by the new technique is amazing and will surely warrant continuing the study of PL process in the narrow gap semiconductors in the coming days. As pointed out (Shao et al. 2006), the most distinct feature distinguishing the modulated step-scan FTIR PL technique from both previous continuous-scan FTIRbased PSD and PSE modulation methods is that, in the step-scan mode there is no Fourier transform required following the data acquisition. It therefore totally resolves the difficulty arising from compromises among the modulation frequency, the scan velocity, and the LIA sampling time constant. The direct results are the obvious advances in either the applicable spectral region, or the experimental time required for a single PL spectrum with a reasonable spectral SNR. To facilitate a simple comparison (Shao et al. 2006), the previous work by Reisinger et al. (1989) and Fuchs et al. (1989), respectively, were taken as good examples of the continuousscan FTIR-based PSD and PSE DM-PL methods. It was noted by Shao et al. (2006) that with a configuration consisting of the 4-kHz chopper frequency and a 0.0355 cm/s scanner velocity employed by Reisinger et al. (1989), the highest applicable spectral range for the continuousscan FTIR-based PSD technique was up to about 5;700 cm1 , which is far from the demands for application to the NIR region. Alternatively, if the entire NIR spectral region were insisted on, the scan velocity must be slowed to 0:0127 cm=s, which is too slow for the scanner to be well controlled. In both cases, the maximal sampling time constant of the LIA is only of the order of magnitude of 1 ms, which for a weak signal is simply too short to ensure phase locking of the LIA! For the continuousscan FTIR-based PSE method, the internal He–Ne laser line Fourier frequency was normally chosen as the carrier frequency for the sake of securing precise phase stability. This means such an arrangement can not be directly applied to a measurement in the spectral region around 630 nm. The experimental time consumed by Reisinger et al. (1989) recording a PL spectrum involves 500 repeated scans for a single spectrum, which requires about 25 min for a scanner velocity of 0.0355 cm/s and a spectral resolution of 10 cm1 . A similar situation was also found for the continuous-scan FTIR-based PSE modulation technique. It produced a PL spectrum with a similar SNR to that of the PSD measurement in a similar duration. 8,000 scans taking a total duration of 140 min were consumed to establish a spectrum with a resolution of 12 cm1 and a reasonable SNR.

2.5.3 Infrared PL from an Sb-Doped HgCdTe Photovoltaic opto-electronic applications of HgCdTe require the formation of a p–n junction. The group V element Sb is expected to act as acceptor in HgCdTe to convert an n-type layer to p-type to achieve a p–n junction. The successful realization of such a conversion processes relies on a knowledge of the doping impurity effectiveness; consequently a study of the Sb impurity doping behavior in HgCdTe is necessary (Chang 1995).

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A series of HgCdTe (x D 0:39) samples with different Sb doping concentrations were used in PL measurements conducted by Chang, et al. Hall measurements were performed with a van Der Pauw configuration under 0.1 T at temperatures of 77 and 300 K. The p-type sample DH04 had a higher doping level. The 77 K carrier concentration measured by the Hall effect was 3:9  1014 cm3 . Sample DH01 has a lower doping level of only 1:3  1013 cm3 again determined by a 77 K Hall measurement. PL and transmission measurements were performed by a Nicolet 800 FTIR spectrometer in the temperature range 4.0–115.0 K. For the PL measurements, an Ar-ion ( D 514:5 nm) laser was used for excitation and a liquid-nitrogen-cooled HgCdTe detector was employed. For the transmission measurements, the signal was detected by either an InSb or a HgCdTe photodiode, with the light beam from a Globar source focused onto the samples’ surface. The spectral resolution of the optical measurements was 2 cm1 in wave numbers (or equivalently about 0.25 meV). Although an infrared transmission spectrum can offer information about the energy band gap, for an accurate determination of Eg the influence of the sample thickness has to be considered. For thin samples near band edge information can be obtained from infrared transmission. Chu et al. (1994) proposed a relation between the absorption coefficient ˛.Eg / at the energy gap Eg : ˛Eg D 65:0 C 1:887 C .8694:0  10:31T /x:

(2.124)

The values of Eg and x of samples can be then derived from the transmission spectra and the aforementioned equation. The composition of the sample DH04 is estimated to be x D 0:38. Figure 2.76 shows the temperature-dependent PL spectra of a p-type Sb-doped HgCdTe sample with a carrier concentration of 3:9  1014 cm3 at 77 K (DH04), under the same laser excitation density (I0 / of about 3 W=cm2 . At 4.2 K, the PL spectrum shown in Fig. 2.76 is dominated by two peaks (labeled A and B). A similar set of PL signals were measured for the sample with the lower doping level

Fig. 2.76 Temperature-dependent PL spectra for an Sb-doped HgCdTe sample

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Fig. 2.77 Temperature-dependent PL spectra for an Sb-doped HgCdTe sample with a low doping concentration

Fig. 2.78 The A peak’s energy as a function of the sample’s temperature. The dotted line is fitted to experimental data by using the formula for Eg .x; T /

(DH01) as shown in Fig. 2.77. The A structure has a sharper PL peak at the higher energy side, while peak B is broader with a FWHM of 18 meV. When the temperature increases, peak B weakens and gradually disappears while peak A is enhanced. Increasing the excitation power intensity causes the integrated emission intensity of peak A to increase much faster than peak B. All our Sb-doped HgCdTe samples exhibit a similar PL structure and similar evolution with temperature and excitation power intensity, therefore their PL peaks can be assigned to the same origin. The dependence of the A peak’s energy as well as the band gap’s energy on temperature is illustrated in Fig. 2.78. It clearly demonstrates that peak A is due to a band-to-band transition above about 50 K where its energy tracts well with the energy gap. But the obvious deviation from the fundamental energy gap below 50 K shows that there must be another transition mechanism responsible for the

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lower temperature PL structure. Since HgCdTe is a pseudobinary II–VI compound semiconductor, local composition fluctuations may exist, which result in local states with an energy Eloc depending on the concentration x as ELoc  x.l  x/, and therefore have a maximum at x D 0:5. We assign the peak A at low-temperatures (below about 50 K) to a localized exciton transition, and obtain an extra localized energy of about 13 meV at a temperature of 4.2 K, which is in good agreement with the earlier results (Lusson et al. 1990). An anomalous behavior of peak A has been found: the integrated intensity of peak A increases from 4.2 to about 20 K, and then decreases with a further temperature increase, which can also be explained within the framework of alloy disorder and potential fluctuations. Therefore, peak A is due to a localized exciton PL below about 50 K, and when the temperature is increased the exciton is gradually delocalized and decomposed, and this peak gradually turns into a band-to-band transition. The peak B is only present at lower temperatures below about 20 K, and its relative integrated PL intensity (IB =I ) under the same experimental conditions increases with the Sb doping concentration. For example, the PL intensity ratio is 0.14 and 0.19 for samples with effective carrier concentrations 1:3  1013 cm3 (DH01) and 3:9  1014 cm3 (DH04) (measured at 77 K) at 15 K and an excitation laser power intensity of 7 W=cm2 . The energy and integrated PL intensity of the peak B as a function of excitation power are depicted in Figs. 2.79 and 2.80. The following characteristics can be observed only under stronger excitation intensities: (1) the peak shifts to higher energy and (2) the integrated intensity of the peak exhibits a tendency to saturate. To our knowledge, these two characteristics can only be fully explained within the theoretical framework of Dı Aı pair transitions. If the small influence of polarization from Dı and Aı is not taken into account, the peak energy for a transition involving randomly distributed donors and acceptors is given to first order by (Lannoo and Bourgoin 1981): E D Eg  ŒED C EA  e 2 =.4"R/;

Fig. 2.79 The B peak’s energy as a function of the excitation power intensity. The dotted line is fitted to the experimental data by using (2.125)

(2.125)

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Fig. 2.80 Intensity of the B peak as a function of excitation power

where ED and EA are the donor and acceptor levels referenced to the conduction and valence bands, respectively, " is the dielectric constant, and R is the separation of the donor–acceptor pair involved in the transition. The final term in parentheses accounts for the Coulomb interaction between the donor and acceptor. Equation 2.125 is valid for donor–acceptor separations greater than about three times of the effective Bohr radius of the bound electron or hole. Minor corrections are needed for smaller separations to account for wave function overlap, but they are not important in this case and will be neglected. If the separation were less than the Bohr radius of isolated carriers, the ionized DC A pair could not bind a free carrier, so the transition probability would rapidly decrease. The characteristics of the B peak can be interpreted from (2.125) following some simple kinetics. The recombination occurs via tunneling; therefore the transition probability decreases exponentially with increasing separation. The photocarriers can recombine through other channels including nonradiative recombination with randomly located donors or acceptors. On the one hand, the PL intensity decreases as R increases, on the other hand the number of carriers, which are located in the same shell dR and emit the same energy, increases as R2 , so there exists a maximum PL intensity when R changes. At low-temperature and low excitation intensity, the term accounting for the Coulomb interaction can be neglected, and the peak energy is E D Eg  .ED C EA /. Increasing the excitation intensity, the concentration of neutral impurities Dı and Aı that are excited is increased, which results in a decreased average separation between Aı and Dı . The transition probability and energy of the emitted photon increases as the separation R is increased, so the PL peak shifts to higher energy. If the excitation intensity is high enough, the average separation between Dı and Aı is a minimum and the PL peak energy position will be a maximum and exhibit a tendency to saturate. The peak energy position dependence on the excitation intensity is (Yu 1977; Binsma et al. 1982): (2.126) EP D EP0 C log.PI =PIo /;

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where Ep and Ep0 are the peak energy positions when the excitation intensity is PI or PI0 , and ˇ is a parameter that increases with an increasing degree of compensation. ˇ is 1.98 for the sample shown in Fig. 2.79. The saturation tendency of the PL intensity with increasing excitation intensity at a given temperature shows that this PL peak is related to centers that can saturate. Schmidt et al. (1992a, b) calculated the dependence of the PL intensity on excitation power intensity in direct gap semiconductors, that shows only Dı Aı PL manifests this obvious saturation tendency providing further evidence of the origin given above for the B peak. The B peak is clearly Sb-doping-related because at 77 K the relative intensity of the B peak increases with the Sb doping concentration, and hence the carrier concentration. Since Sb is a group Va element and the doped samples are p-type, considering the usual hydrogen-atom-like donor level is about 1.5 meV in Hg1x Cdx Te .x D 0:39/, an Sb-doping-related acceptor level at about 30 meV, relative to the top of valence band, is deduced. For the PL spectra recorded at higher temperature (above about 77 K), a weak feature on the low energy side of the A peak can be identified, which has been assigned as due to a bound-to-free transition. The impurity level involved is at about 30 meV. Because the hydrogen-atom-like shallow donor level is only about 2–3 meV in Hg1x Cdx Te .x D 0:39/, it can no longer bind electrons when the temperature is increased. Then the Dı Aı transition is replaced by a bound-to-free transition. The transition from an Sb acceptor to the conduction band has been observed in PL spectra. This result is in agreement with that obtained from Dı Aı and also with that estimated from a hydrogen atom analogy. In summary, Sb-doped HgCdTe samples have been investigated by infrared FTIR PL spectroscopy and a localized exciton, Dı Aı , and band-to-band and bound-to-free transition related PL structures are observed. An Sb-doping-related acceptor level of about 30 meV at 4.2 K is obtained from these PL spectra.

2.5.4 Infrared PL in As-doped HgCdTe Epilayers MBE-grown Hg1x Cdx Te thin films are now a key material system for infrared photodetector applications due to their high performance. Photovoltaic infrared photodetector structures possess rapid responsivities and hence ensure high-speed direct detection and even heterodyne detection. Because this structure can work under zero bias, it reduces power consumption. In addition this structure is suitable for realizing focal plane arrays. For a p-on-n HgCdTe structure, a low surface leakage current and n-type minority carriers with long lifetime are predicted. Excellent detection efficiency is found for these structures (Bubulac et al. 1987; Arias et al. 1989; Harris et al. 1991; Shin et al. 1993). By choosing proper growth conditions, such as decreasing the growth temperature and increasing the Hg partial pressure, n-type Hg1x Cdx Te thin films with superior properties can be obtained. To fabricate photovoltaic infrared detectors, As ion implantation is often used for doping. Under a high Hg partial pressure

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and with a suitable annealing temperature, As will occupy Te sites (Maxey et al. 1993) to yield the p-type surface layer of a p-on-n structure. Therefore, it is necessary to investigate the As-doped properties of Hg1x Cdx Te. The samples used by Chang (1995) were prepared by first growing a 5-m-thick CdTe buffer layer on a GaAs substrate, then growing an n-type Hg1x Cdx Te film on the buffer layer. Then As-ions were implanted and the sample annealed under suitable time and temperature conditions to produce a 3-m-thick p-type region at the surface. The samples were put into a dewar filled with liquid Helium. An ArC laser ( D 514:5 nm) illuminated the sample. PL signals were collected by a parabolic mirror and sent into an FTIR spectrometer for analysis. Photocurrent and transmission experiments were also carried out using the same FTIR spectrometer. To make a comparison, the samples were measured again after a treatment by dilute Hydrobromil acid solutions for 1.5 min. Then a second comparative experiment was conducted. The PL signals from two Hg1x Cdx Te samples annealed at temperatures of 400 and 550ı C but with a similar x and ion implantation conditions as before, were also recorded. The transmission spectra of another sample (450ı C annealing temperature) before and after etching are displayed in Fig. 2.81. From the energetic positions of the interference peaks, the thickness d of the Hg1x Cdx Te epitaxial layers can be estimated and are 10 and 7 m, respectively. Furthermore, the concentration x of the samples near their surfaces can also be determined to be approximately 0.39 (Chu et al. 1983). By using the relation between the band gap Eg and temperature T (4.28 K) (Chu et al. 1994), the band gap at different temperatures can be calculated, which locates the position of the PL peak corresponding to a band-to-band transition. Figure 2.82 shows the photocurrent spectra of an infrared detector linear array made on this HgCdTe epilayer. These results are similar to those of the transmission spectra. Figure 2.83 shows the PL spectra of a sample taken at an identical excitation power but at different temperatures. Four PL peaks are clearly seen, which are labeled A, B, C, and D.

Fig. 2.81 Transmission spectra of a sample recorded before (solid lines) and after (dotted line) etching

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Fig. 2.82 Photocurrent spectra of a photosensitive unit of a p-on-n infrared detector linear array under zero bias. The unit was made on a HgCdTe epilayer after an As-ion implantation and subsequent anneal

Fig. 2.83 Temperaturedependent PL spectra of a HgCdTe sample annealed at 450ı C after As-ion implantation. The dotted line refers to the PL spectrum of a HgCdTe sample annealed at 400ı C

In Fig. 2.84, the relation between the peak intensity IP:PL and the excitation power PI is given for the spectra depicted in Fig. 2.83. It is shown that the peak intensity as a function of the excitation power is: IPPL D CPIv ;

(2.127)

where C is a constant, and v is the power exponent. From the value of v, we can determine approximately the transition mechanisms responsible for the PL peaks. The energy of peak A is close to Eg . Its intensity is weak at low-temperatures (T < 20 K) and gets stronger at higher temperatures (T > 20 K). There are no further PL peaks appearing on the high energy side of peak A. Therefore, peak A can be interpreted as the PL peak due to band-to-band transitions. The other peaks are identified based on the interpretation of peak A. The PL spectrum of sample 1 after

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111

Fig. 2.84 Integrated intensity of the main PL peaks as a function of the excitation power. The results for the sample before and after etching are given in (b) and (a), respectively

Fig. 2.85 Temperature-dependent PL spectra for samples after etching

etching is given in Fig. 2.85. The thickness of the sample was reduced to 3 m. In general, for Hg1x Cdx Te using the same injection dose, but after annealing, according to secondary ion mass spectrometry (SIMS) data, the impurity density in a layer 3 m under the surface decreases by 2–3 orders relative to the injection dose. Under this condition, the dose injected impurity layer is basically removed. It is obvious from Fig. 2.85 that the peaks B (unobservable) and D are reduced and peak C is

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enhanced relative to peak A. Thus the peaks B and D are related to the As impurity and the peak C is unrelated to the As impurity. Figure 2.84 gives the integrated intensity of main PL peaks before and after etching, as a function of the excitation power. The energy and the feature of the peak A are almost unchanged before and after etching. Therefore, it is still related to a band-to-band transition. The energy of peak C as a function of temperature is similar to that of peak A. Moreover, as the excitation power increases, the energy of the peak C does not change appreciably. The peak intensity as a function of excitation power is depicted in Fig. 2.84. The value of for peak C is slightly smaller than that of peak A. As a result, peak C may originate from a bound exciton. Its peak energy is 16–17 meV lower than that of the peak A. For Hg1x Cdx Te with x D 0:39, the binding energy of an exciton is approximately 1.5 meV, which does not account for the observations. Thus, there is an impurity level involved and its energy is in the range of about 14.5–15.5 meV. By comparing the above result to those reported in the other references (Hunter and McGill 1981, 1982; Tomm et al. 1990, 1994) the peak C can be ascribed to the PL of an acceptor level bound exciton due to a Hg vacancy. From the temperature and excitation power dependences of their peak energy and intensity, the B and D peaks are found to be related to bound excitons. The B peak is strong for the sample before etching, but not distinguishable after etching. The C peak is not so strong before etching, but enhanced significantly after etching. It is believed that before removing the implanted layer by etching, As impurities occupy Hg vacancy sites and hence the density of Hg vacancies is reduced. Therefore, the intensity of the C peak is enhanced and the peak B is reduced by etching. It is concluded that the residual low intensity B PL peak detected after annealing is a donor level bound exciton of an As occupying a cation site. According to the energy of the B peak and the exciton bound energy in Hg1x Cdx Te.x D 0:39/, it can be inferred that As occupying a cation site has a donor level of 8.5 meV. The mechanism responsible for the D peak is complicated. According to a comparison of the results before and after etching, the D peak is strong before etching and reduced after etching. The D peak is regarded as related to the ion implantation. Figure 2.84 gives the peak intensity as a function of the excitation power for the sample after etching. It is clear that the D peak saturates as the excitation power increases. However, a blue shift of the D peak is detected for low excitation power. These are typical features of a D–A pair PL (Schmidt et al. 1992a, b). Thus the D peak can be ascribed to a PL peak due to a D–A pair. However, if the donor and acceptor are highly compensated in these samples, and the change with excitation power is not significant, the D–A pair PL would probably not be observable. After being etched, the concentration of As decreases by 2–3 orders, which results in a decrease of the compensation, and hence the D peak Fig. 2.84 may indeed represent a D–A pair feature. A further comparison was conducted in an effort to validate the proposed origin of the D peak. The PL spectra of samples annealed at a temperature of 400ı C are depicted in Fig. 2.83. From these spectra, only the peaks A, B, and C are observable. The D peak is almost undistinguishable. It may be concluded that the D peak is related not only to the ion implanted As, but also to the annealing temperature.

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For the implanted As in Hg1x Cdx Te, the As impurity will occupy a Te site as an acceptor with large probability when the samples are annealed at a high annealing temperature and Hg partial pressure. Therefore, the D peak is a D–A pair PL related to the As donor when occupying a cation site, and becomes an acceptor level when it occupies a Te site after the As ion implantation and an annealing process. The contributing donor level for the PL is supplied by some As still occupying cation sites. From the energy of the D peak and the donor level due to an As occupying a cation site (8.5 meV), it is concluded that the As acceptor on a Te site in Hg1x Cdx Te.x D 0:39/ results in an acceptor level at approximately 31.5 meV. In summary, the impurity behavior of As-doped MBE-grown HgCdTe films were investigated by using PL spectroscopy. For As ion-doped Hg1x Cdx Te.x D 0:39/ samples with different annealing temperatures, the PL peaks related to band-toband, bound exciton, and D–A pair transitions were detected. Two energy levels related to As ion implantation were determined. The donor level due to an As occupying a cation site is located at approximately 8.5 meV below the bottom of the conduction band. The acceptor level due to an As occupying a Te site is located at approximately 31.5 meV above the top of the valance band. With the help of these PL spectra, the amphoteric behavior of high concentrations of implanted As ions were directly observed.

2.5.5 Behavior of Fe as an Impurity in HgCdTe Recently, doping of transition and rare earth elements into Hg1x Cdx Te, has been carried out. By using heavy doping to form four element alloys, we can strengthen the weak Hg bond to be more appropriate for device applications. Also, in device technology of Hg1x Cdx Te, some Fe contamination is unavoidable. The behavior of Fe-doped Hg1x Cdx Te has been examined by infrared transmission spectroscopy, PL spectroscopy and Hall measurements. The results indicate that Fe impurities lead to a donor level which is about 80 meV below the bottom of the conduction band. In spite of exhibiting no electrical activity at low-temperature (T < 180 K), Fe impurity centers can become the main nonradiative recombination mechanism for nonequilibrium carriers. Thus, it can reduce the lifetime of nonequilibrium carriers to adversely influence Hg1x Cdx Te device performance. The Fe-doped Hg1x Cdx Te.x D 0:31/ has been cut from bulk material grown by the moving heater method (Chang et al. 1997). In these samples the doping concentration of Fe can be above 1018 cm3 . The Van der Paul method was applied in a Hall measurement. The measurement was done from 77 to 300 K and with a magnetic density of 0.1 T. Infrared transmission spectroscopy was measured from 1.9 to 300 K by using an Oxford 104 liquid Helium Dewar and a globar light source. To reduce the thermal background interference, the double modulation technique was used to obtain highly sensitive PL spectra. PL spectra were measured from 3.9 to 300 K.

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Fig. 2.86 Infrared transmission spectra of an Fe-doped Hg1x Cdx Te.x D 0:31/ bulk sample at different temperatures. The dotted line in the inset shows the calculated transmittance taking into account the Urbach tail absorption and ionized impurity absorption

Figure 2.86 shows the infrared transmission spectra of an Fe-doped Hg1x Cdx Te at different temperatures. We can clearly observe impurity related absorption below the Urbach tail absorption at higher temperatures. This absorption structure is obvious at room temperature, becomes weaker with decreasing temperature, and disappears by a temperature of 3:9 K. From this temperature dependence, we can conclude it is due to an ionized impurity. Absorption is enhanced as the temperature increases and the impurities thermally ionize. Because the density of states of impurities is much smaller than the density of states of the conduction and the valence bands, its absorption coefficient is much smaller than that of band-to-band transitions. It only takes the form of an absorption shoulder appended onto the Urbach absorption tail. From a combination of the transitions from ionized donor impurity to the conduction band and band-to-band absorption, the infrared transmission spectra can be fitted by using the formula (4.2–300 K): Tr D

.1  R/2 exp.˛d / ; 1  R2 exp.2˛d /

(2.128)

where Tr is the transmittance, ˛ the absorption coefficient, d the thickness of the sample, d D 0:75 mm, and R is reflectance. R for normal incidence is written as: RD

.n  1/2 C k 2 ; .n C 1/2 C k 2

(2.129)

where k is the extinction coefficient and n is the index of refraction. n is given by the empirical formula (Liu et al. 1994): n.; T / D A C

B C D2 : 1  .C =/2

(2.130)

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115

A, B, C, and D are given in Eq. (4.30) of Vol. I, Sect. 1, Chap. 4. .m/ is the wavelength related to the photon energy „! (meV) via:  D 1:24  103 =.„!/;

(2.131)

and the extinction coefficient k is written as: kD

 ˛: 4

(2.132)

In fact, the influence of k is very small. In the impurity absorption distribution the main parameter in the fitting calculation is ˛ and it can be regarded as a superposition of two absorption mechanisms: ˛ D ˛im C ˛in ; (2.133) where ˛in is the intrinsic inter-band absorption coefficient, and ˛im is the ionized impurity absorption coefficient. ˛in near the absorption edge is given by an empirical formula:   ı .E  E0 / : ˛in D ˛0 exp (2.134) kB T The parameters of (2.134) are in Eq. (4.120) of Vol. I, Sect. 4.3. For the transition from an ionized donor impurity to the valence band, the absorption coefficient ˛im can be obtained from the proportionality expression (Seeger 1985): p ND „!  .Eg  "D / ˛im „! / : (2.135) gD exp Œ."D  EF /=kB T  Furthermore, (2.135) can be written as a equality: ˛im

p C „!  .Eg  "D / ; D „! .gD exp Œ."D  EF /=kB T /

(2.136)

where ND is the concentration of donor impurities, „! the photon energy, Eg the band gap, kB the Boltzmann constant, gD the energy level degeneracy of an Fe donor impurity, "D the donor energy, "D is the donor ionization energy, "D D Eg  "D , and C is a fitting parameter. The Fermi level EF can be calculated from the impurity concentration obtained from a Hall measurement. The calculated results from transmission spectra at 300 K are given in the inset to Fig. 2.86. In the fitting calculation, only "D ; "D ; x; C , and gD are adjustable parameters. The absorption edge of the transmission spectra is determined by the concentration x. The impurity absorption portion is mainly due to the impurity ionization energy. C is a proportionality parameter. The calculation is not sensitive to gD . In general, gD D 2. After the fitting is done, the composition x is 0.31 and the ionization energy "D is 80 meV. As a result, the donor level deduced for the Fe impurity in Hg1x Cdx Te .x D 0:31/ lies at about 80 meV below the conduction band edge. This energy is near Eg =4 so it is a deep level.

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Fig. 2.87 Hall measurement results for an Fe-doped Hg1x Cdx Te.x D 0:31/ at 77 and 300 K. The solid line is calculated using the measured intrinsic carrier concentration. The difference between the experimental and calculated results can be explained as due to the thermally induced carrier ionization of the Fe-related level

Because the Fe-related level is a deep level, it has little influence on the electrical conductivity of the material at low-temperature. The Hall measurement results support this position. Figure 2.87 gives the results of Hall measurements between 77 and 300 K. By using the Hall coefficients in the flat region at low-temperature, we can calculate the effective shallow donor concentration which is 1:06  1014 cm3 . The carrier concentration is calculated using (2.137) for an Fe donor contribution  : of ND  /; n2i D n.n  ND

(2.137)

where the intrinsic carrier concentration ni is given by (2.138) (Chu et al. 1991). A detailed derivation of this formula is given in Sect. 3.1. 1     Eg 3:25kB T 3=2 3=4 Eg T 3=2 1 C 1:9Eg exp ni D 9:56  1014 1 C Eg 2kB T (2.138)

From the result calculated in Fig. 2.87, we find that when the temperature exceeds 180 K, the carrier concentration obtained from experiments is higher than that calculated. This occurs because the Fe impurities ionize at the higher temperature. Then electrons are excited from the impurity levels to the conduction band where they contribute to the electrical transport. This allows some electrons to transit from the valence band to the ionized Fe levels. Thus, ionized impurity absorption will occur at these higher temperatures. In this case, we can observe an absorption shoulder in the infrared transmission spectra. At lower temperatures, this absorption is weak and not observed because the chance of impurity ionization is small. While an Fe impurity has very little effect on electrical transport at lowtemperature and is not clearly observed in the infrared transmission spectra, it could have an effect on the lifetime of nonequilibrium carriers and in the PL spectra taken at low-temperature. A DM-PL spectrum is given in Fig. 2.88. Only one PL

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117

Fig. 2.88 DM-PL spectra of an Fe-doped HgCdTe sample at 4.2 K. The excitation power density is 8 W=cm2

peak can be seen and its energy is independent of the excitation power. Furthermore, the integrated intensity of the PL peak shows no tendency to saturate with increased excitation power. Therefore, we think this single peak with its high energy is due to a band-to-band transition or a free exciton (Tomm et al. 1990, 1994). Because the bond energy of the free exciton in HgCdTe is small, less than 3 meV (Brice and Capper 1987) it lies within the band width of the observed peak. In any case, the PL peak is unrelated to the Fe doping because the Fe-related level is deep, equal to 1/4 of the energy gap it would produce a peak well below the one that is observed. No other PL peak is found in this energy position. However, from the following analysis it can be seen that Fe at low-temperature contributes a nonradiative recombination mechanism for nonequilibrium carriers, which has a significant influence on device applications. The integrated intensity of the PL peak decreases as the temperature is increased higher than 3.9 K. It indicates that there is a thermally activated nonradiative recombination mechanism. To investigate the thermally activated quenching mechanism of the PL peak, we fit the integrated intensity of the PL peak to a function of temperature when the temperature exceeds 60 K. The fitting formula used is: 1   E ; (2.139) IPL D I0 1 C C exp  kB T where IPL is PL intensity, I0 and C constants, and E is the thermal activation energy of the PL quenching process. The best-fit yields an activation energy E of 78.3 meV, which is consistent with the results calculated from infrared transmission spectra (80 meV). It indicates that an Fe-related level is the main cause of the PL quenching. Because the Fe-related level is a deep level, it can be the intermediate step of an indirect recombination mechanism for the nonequilibrium carriers. Then, it serves as an effective nonradiative center and has a significant effect on the rate of the recombination of photo-excited nonequilibrium carriers.

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Ye (1995) measured the lifetime of the nonequilibrium carriers of an Fe-doped HgCdTe sample by using a microwave reflectance technique. They found the averaged lifetime is 0:39 s, which is shorter than that of n-type materials of high quality. When they measured a surface distribution of the lifetimes, they found the maximum is 1:84 s, and the minimum is 1:08 s. The averaged relative deviation of all the test points is less than 10%, which represents a good uniformity (Ye 1995). Based on a topography analysis technique, Cai et al. (1994, 1995) found dislocations in bulk HgCdTe crystals resulting from stress introduced in the process of growth and post-growth treatments. These processes destroy the crystal symmetry and induce deep levels in the band gap to form recombination centers. The distribution of the dislocations is generally nonuniform, which leads to a discreteness of the lifetime distribution of the samples. Doping can improve the yield stress of semiconductor materials (Farges 1990). Fe-doping results in a strong interaction between the Fe atoms and the atoms in HgCdTe, which improves the yield stress of HgCdTe materials. It reduces the dislocation occurrence probability and improves the lifetime in the samples. These problems need further study. By using optical and electrical methods, the behavior of an Fe-doped Hg0:31 Cd0:69 Te crystal was investigated. The relation between the PL intensity and temperature was established as shown in Fig. 2.89. With this relation, a thermally activated nonradiative recombination centers properties were clarified in the Fe-doped samples, which has a donor level at about 1=4 Eg . This value is consistent with that of the deep donor level observed in the infrared transmission spectra. The results of Hall measurements are also explained. The experimental results indicate that Fe-doping has little effect on the low-temperature electrical properties of these materials. However, the Fe-related level .Eg =4/ is the main recombination center at higher temperatures and leads to recombination of the nonequilibrium carriers in these materials.

Fig. 2.89 The integrated PL intensity vs. temperature for an Fe-doped HgCdTe sample (square points). A fitted result for temperatures higher than 60 K is give by the solid line. The slope of the solid line is the thermal activation energy related to PL quenching. A best fit yields an energy of 78.3 meV

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Capper P (1989) Bridgman growth of Hg1x Cdx Te:A review. Prog. Cryst Growth Charact 19:259–293 Capper P (1991) A review of impurity behavior in bulk and epitaxial. J Vac Sci Technol B 9:1667 Capper P, Gosney JJG, Jones CL, Kenworthy I, Roberts JA (1985) Acceptor doping of bridgmangrown Cdx Hg1x Te. J Cryst Growth 71:57–65 Casselman TN (1981) Calculation of the auger lifetime in p-type Hg1x Cdx Te. J Appl Phys 52:848–584 Casselman TN, Sher A, Silberman J, Spicer WE, Chen AB (1983) On the determination of the energy band offsets in Hg1x Cdx Te heterojunctions. J Vac Sci Technol 1:1692–1695 Chadi J (1977) Localized-orbital description of wave functions and energy bands in semiconductors. Phys Rev B 16:3572–3578 Chang Y (1995) Ph.D. thesis, Shanghai Institute of Technical Physics Chang Y, Chu JH, Tang WG, Shen WZ, Tang DY (1997) Spectroscopic and electrical investigation on Fe-doped Hg1x Cdx Te. Chin J Semicond 18:258–263 Chen AB (1977) Simple brillouin-zone scheme for the spectral properties of solids. Phys Rev B 16:3291–3302 Chen AB, Sher A (1980) Electronic structure of III–V semiconductors and alloys using simple orbitals. Phys Rev B 22:3886–3896 Chen AB, Sher A (1981a) Electronic structure of pseudobinary semi-conductor alloys Alx Ga1x As, GaPx As1x , and Gax In1x P. Phys Rev B 23:5360–5374 Chen AB, Sher A (1981b) Calculation of the electronic properties of pseudobinary semiconductor alloys. Phys Rev B 23:5645–5648 Chen AB, Sher A (1985) Sensitivity of defect energy levels to host band structures and impurity potentials in CdTe. Phys Rev B 31:6490–6497 Chen MC, Dodge JA (1986) Electrical properties of antimony-doped p-type Hg0:78 Cd0:22 Te liquidphase-epitaxy films. Solid State Commun 59:449–452 Chen MC, Tregilgas JH (1987) The activation energy of copper shallow acceptors in mercury cadmium telluride. J Appl Phys 61:787–789 Chen W (1990) Master thesis, Shanghai Institute of Technical Physics Chen YP, Zheng GZ, Gong YQ, Guo SL, Chen JX, Tang DY (1990) Composition dependence of hot electron effect in Hg1x Cdx Te. Semicond Sci Technol 5:S304–306 Cheung DT (1985) An overview on defect studies in MCT. J Vac Sci Technol A 3:128–130 Chu JH (1988) Fachkolloquium “II-VI-Halbleiter”. Jahrestagung der DGKK, Karlsruhe, Marz Chu JH, Xu SC, Tang DY (1983) Energy gap versus alloy composition and temperature in Hg1x Cdx Te. Appl Phys Lett 43:1064–1066 Chu JH, Mi ZY, Tang DY (1991) Intrinsic absorption spectroscopy and related physical quantities of narrow-gap semiconductors Hg1x Cdx Te. Infrared Phys 32:195–211 Chu JH, Mi ZY, Sizmann R, Koch F, Wollrab R, Ziegler J, Maier H (1992) Influence of resonant defect states on subband structures in Hg1x Cdx Te. J Vac Sci Tech B 10:1569–1573 Chu JH, Li B, Liu K, Tang DY (1994) Empirical rule of intrinsic absorption spectroscopy in Hg1x Cdx Te. J Appl Phys 75:1234–1235 Cole A, Carey GP, Silberman JA, Spicer WE, Wilson JA (1985) Surface and bulk structural defects in Hg1x Cdx Te. J Vac Sci Technol A 3:206–211 Collins RT, McGill TC (1983) Electronic properties of deep levels in p-type CdTe. J Vac Soc Techol A 1:1633 Cotton VA, Wilson JA (1986) Effects of ion implantation on deep electron traps in Hg0:7 Cd0:3 Te. J Vac Sci Technol A 4:2177–2180 Datsenko LI, Skorokhod M, Kislovski EN et al (1985) Inorg Mater 20:1575 Dean BE, Johnson CJ, McDevitt SC, Neugebauer GT, Sepich JL, Dobbyn RC, Kuriyama M, Ellsworth J, Vydyanath HR, Kennedy JJ (1991) Correlation of HgCdTe epilayer defects with underlying substrate defects by synchrotron X-ray topography. J Vac Sci Technol B 9: 1840–1846 Destefanis GL (1985) Indium ion implantation in Hg0:78 Cd0:22 Te=CdTe. J Vac Sci Technol A 3:171–175

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Jones CE, Nair V, Lindquist JL, Polla DL (1982) Effects of deep-level defects in Hg1x Cdx Te provided by DLTS. J Vac Sci Technol 21:187–190 Jones CL, Capper P, Quelch MJT (1983) The properties of gold in Bridgman grown Cdx Hg1x Te. J Cryst Growth 64:417–432 Jones H (1934) Proc Roy Soc A 144:225 Kane EO (1976) Gaussian representations of covalent wave functions; silicon. Phys Rev B 13:3478–3483 Keyes RJ (1977) Optical and infrared detectors. Springer, Berlin Kinch MA, Borrello SR (1975) 0.1 eV HgCdTe photodetectors. Infrared Physics 15:111–124 Kinch MA, Brau MJ, Simmons A (1973) Recombination mechanisms in 8–14- HgCdTe. J Appl Phys 44:1649 Klauer S, W¨ohlecke M, Kapphan S (1992) Influence of H-D isotopic substitution on the protonic conductivity of LiNbO3 . Phys Rev B 45:2786 Kobayashi A, Sankey OF, Dow JD (1982) Chemical trends for defect energy levels in Hg1x Cdx Te. Phys Rev B 25:6367–6379 Krishnamurthy S, Berding MA, Yu ZG (2006) Minority carrier lifetimes in HgCdTe alloys. J Electron Mater 35:1369–1378 Kurilo IV, Kuchma VI (1982) Twinning in CdTe and Cdx Hg1x Te crystals. Inorg Mater 18:479 Kurtz SR, Bajaj J, Edwall DD, Irvine SJC (1993) Infrared photoluminescence characterization of long-wavelength HgCdTe detector materials. Semicond Sci Technol 8:941–945 Lang DV (1974) Deep-level transient spectroscopy: a new method to characterize traps in semiconductors. J Appl Phys 45:3023 Lannoo M, Bourgoin J (1981) Point defects in semiconductors I: theoretical aspects. Springer, New York, Chap. 2 Li B, Gui YS, Chen ZH, Ye HJ, Chu JH, Wang SL, Ji RB, He L (1998) Study of impurity states in p-type Hg1x Cdx Te using far-infrared spectroscopy. Appl Phys Lett 73:1538 Liu K, Chu JH, Tang DY (1994) Composition and temperature dependence of the refractive index in Hg1x Cdx Te. J Appl Phys 75:4176 Lopes VC, Syllaios AJ, Chen MC (1993) Minority carrier lifetime in mercury cadmium telluride. Semicond Sci Technol 8:824–841 Losee DL (1972) Admittance spectroscopy of deep impurity levels: ZnTe Schottky barriers. Appl Phys Lett 21:54 Losee DL (1975) Admittance spectroscopy of impurity levels in Schottky barriers. J Appl Phys 46:2204 Lucovsky G (1965) On the photoionization of deep impurity centers in semiconductors. Solid State Commun 3:299–302 Lusson A, Fuchs F, Marfaing Y (1990) Systematic photoluminescence study of Cdx Hg1x Te alloys in a wide composition range. J Crystal Growth 101:673–677 Maxey CD, Whiffin PAC, Easton BC (1991) MOVPE growth and characterization of doped Cdx Hg1x Te structures. Semicond Sci Technol 6:c26–c30 Maxey CD, Gale LG, Clegg JB, Whiffin PAC (1993) Doping studies in MOVPE-grown Cdx Hg1x Te. Semicond Sci Technol 8:s183–s196 Mirsky U, Shechtman D (1980) Transmission electron microscopy and X-ray topography study of mercury-cadmium-telluride. J Electron Mater 9:933–943 Mosser V, Sizmann R, Koch F, Ziegler J, Maier H (1988) Quantum physics of the surface layer capacitance for narrow-gap HgCdTe. Semicond Sci Technol 3:808–812 Mott N, Jones H (1936) The theory of the properties of metals and alloys. Clarendon, Oxford Murakami S, Okamoto T, Maruyama K, Takiqawa H (1993) Iodine doping in mercury cadmium telluride (Hg1x Cdx Te) grown by direct alloy growth using metalorganic chemical vapor deposition. Appl Phys Lett 63:899 Myles CW (1987) The 1987 US workshop on the Physics and Chemistry of HgCdTe. New Orleans, LA, PO/DI-31 Nicollian EH, Brews TR (1982) MOS physics and technology. Wiley, New York Petersen PE (1970) Auger recombination in Hg1x Cdx Te. J Appl Phys 41:3465

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Petersen PE (1983) In: Willardson RK, Beer AC (eds) Semiconductors and semimetals, vol 18. Academic, New York, chap. 6 Petrov VI, Gareeva AR (1988) Bull Acad Sci USSR Phys Ser (USA) 52:110 Polla DL, Jones CE (1980a) Admittance spectroscopy of deep levels in Hg1x Cdx Te. J Appl Phys 51:6233 Polla DL, Jones CE (1980b) Deep level transient spectroscopy in Hg1x Cdx Te. Solid State Commun 36:809 Polla DL, Jones CE (1981) Deep level studies of Hg1x Cdx Te. I: narrow-band-gap space-charge spectroscopy. J Appl Phys 52:5118 Polla DL, Aggarwal RL, Mroczkowski JA, Shanley JF, Reine MB (1982) Observation of deep levels in Hg1x Cdx Te with optical modulation spectroscopy. Appl Phys Lett 40:338 Pratt RG, Hewett J, Capper P, Jones CL, Quelch MJ (1983) Minority carrier lifetime in n-type Bridgman grown Hg1x Cdx Te. J Appl Phys 54:5152 Pratt RG, Hewett J, Capper P (1986) Minority-carrier lifetime in doped and undoped n-type Cdx Hg1x Te. J Appl Phys 60:2377 Reisinger AR, Roberts RN, Chinn SR, Myersll TH (1989) Photoluminescence of infrared-sensing materials using an FTIR spectrometer. Rev Sci Instrum 60:82 Rosback JP, Harper ME (1987) Doping and composition profiling in Hg1x Cdx Te by the graded capacitance–voltage method. J Appl Phys 62:1717 Rosemeier RG (1983) Real-time X-ray topography: applications to bulk HgCdTe materials. J Vac Sci Technol A 1:1656–1660 Ryssel H, Lang G, Biersack JP, Muller K, Kruger W (1980) Ion implantation doping of Cd0:2 Hg0:8 Te for infrared detectors. IEEE Trans Electron Devices 27:58–62 Sasaki T, Oda N, Kawano M, Sone S, Kanno K, Saga M (1992) Mercury annealing effect on the electrical properties of HgCdTe grown by molecular beam epitaxy. J Cryst Growth 117: 222–226 Schaake HF (1986) Ion implantation damage in Hg0:8 Cd0:2 Te. J Vac Sci Technol A 4:2174–2176 Schaake HF (1988) Proc SPIT-Int Soc Opt Eng (USA) 946:186 Schacham SE, Finkman E (1985) Recombination mechanisms in p-type HgCdTe: freezeout and background flux effects. J Appl Phys 57:2001 Schmidt T, Lischka K, Zulehner W (1992a) Excitation-power dependence of the near-band-edge photoluminescence of semiconductors. Phys Rev B 45:8989–8994 Schmidt T, Daniel G, Lischka K (1992b) The excitation power dependence of the near band edge photoluminescence of II–VI semiconductors. J Cryst Growth 117:748–752 Schmit JL, Stelzer EL (1969) Temperature and alloy compositional dependences of the energy gap of Hg1x Cdx Te. J Appl Phys 40:4865 Scott W, Stelzer EL, Hager RJ (1976) Electrical and far-infrared optical properties of p-type Hg1x Cdx Te. J Appl Phys 47:1408 Seeger K (1985) Semiconductor physics: an introduction. Springer, Berlin Shao J, Lu W, L¨u X, Yue FY, Li ZF, Guo SL, Chu JH (2006) Modulated photoluminescence spectroscopy with a step-scan Fourier transform infrared spectrometer. Rev Sci Instrum 77:063104 Shen J, Chen JZ, Chen YQ (1980) Infrared Phys Technol 1:1 Shen XC (1992) Optical properties of semiconductor. Science, Beijing Shen XC (1994) Prog Phys (Chinese) 4:452 Sher A, Hoffman HJ, Su P, Tsuo YH (1983) Techniques for improving the Si–SiO2 interface characterization. J Appl Phys 54:5183 Shin SH, Chu M, Vanderwyck AHB, Lanir M, Wang CC (1980) Electrical properties of as-grown Hg1x Cdx Te epitaxial layers. J Appl Phys 51:3772 Shin SH, Arias JM, Edwell DD et al (1991) Proc 1991 US workshop on chemistry of MCT and II–VI compounds 69 Shin SH, Arias JM, Zandian M, Pasko JG, Bubulac LO, DeWames RE (1993) Annealing effect on the P-type carrier concentration in low-temperature processed arsenic-doped HgCdTe. J Electron Mater 22:1039–1047

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Sladek RJ (1958) Magnetoresistance oscillations in single-crystal and polycrystalline indium arsenide. Phys Rev 110:817–826 Stahle CM, Helms CR, Simmons A (1987) Thermal stability of the anodic oxide/Hg1x Cdx Te interface. J Vac Sci Technol B 5:1092–1096 Swarts CA, Daw MS, McGill TC (1982) Bulk vacancies in Cdx Hg1x Te. J Vac Sci Technol 21:198 Swink LW, Brau MJ (1970) Rapid, nondestructive evaluation of macroscopic defects in crystalline materials: the laue topography of (Hg, Cd) Te. Metall Mater Trans B 1: 629–634 Sze SM (1969) Physics of semiconducting devices. Wiley, New York, p 429 Tang DY (1974) Infrared Phys Technol 16:345 Tang DY (1976) Infrared Phys Technol 25–26:53 Tang WG, Chang Y, Shen WZ (1995) Basic applications studies of HgCdTe materials and devices, 1995 collections of the theses. Shanghai Institute of Technical Physics, Shanghai, p 108 Tomm JW, Herrmann KH, Yunovich AE (1990) Infrared photoluminescence in narrow-gap semiconductors. Phys Stat Sol A 122:11–42 Tomm JW, Herrmann KH, Hoerstel W, Lindstaedt M, Kissel H, Fuchs F (1994) On the nature of the excitonic luminescence in narrow-gap Hg1x Cdx Te .x Š 0:3/. J Cryst Growth 138:175–181 Tsau GH, Sher A, Madou M, Wilson JA, Cotton VA, Jones CE (1986) Low-frequency admittance measurements on the HgCdTe/Photox SiO2 interface. J Appl Phys 59:1238 Vodop’yanov LK, Kozyrev SP, Spitsyn AV (1982a) Ion implantation of impurities in n-type Hg0:8 Cd0:2 Te. I Group II ions MgC ; ZnC ; CdC . Sov Phys Semicond (USA) 16:502–506 Vodop’yanov LK, Kozyrev SP, Spitsyn AV (1982b) Ion implantation of impurities in n-type Hg0:8 Cd0:2 Te. II. group III ions AlC and GaC . Sov Phys Semicond (USA) 16:626–629 Vydyanath HR (1990) Amphoteric behaviour of group V dopants in (Hg, Cd)Te. Semicond Sci Technol 5:S213–S216 Vydyanath HR (1991) Mechanisms of incorporation of donor and acceptor dopants in (Hg, Cd)Te alloys. J Vac Sci Technol B 9:1716 Vydyanath HR, Kr¨oger FA (1982) Doping behavior of iodine in Hg0:8 Cd0:2 TeC . J Electron Mater 11:111–131 Vydyanath HR, Donovan JC, Nelson DA (1981) Lattice defects in semiconducting Hg1x Cdx Te Alloys III–defect structure of undoped Hg0:6 Cd0:4 Te. J Electrochem Soc 128:2625–2629 Wang J (1989) PhD thesis. Shanghai Institute of Technical Physics Wang SW, Tang DY, Tong FM (1991) Research and progress in semiconductor devices II. Science, Beijing Wang Y, Cai Y, He YC et al (1992) Infrared Technol 14:1 Wang ZX, Wei XJ, Lai DS et al (1984) Laser & Infrared 1:53 Willardson RK, Beer AC (1981) mercury cadmium telluride. Semiconductors and semimetals, vol 18. Academic, New York Yang JR (1988) PhD thesis. Shanghai Institute of Technical Physics Ye RQ (1995) Basic applications studies of HgCdTe materials and devices, 1995 collections of the theses. Shanghai Institute of Technical Physics, Shanghai, p 165 Yoshikawa M, Ueda S, Maruyama K, Takigawa H (1985) The behavior of oxygen in HgCdTe. J Vac Sci Technol A 3:153–155 Yu F, Xu S, Zhang S (1990) Infrared Phys 30:61 Yu FJ (1976) Infrared Phys Technol 25–26:30 Yu PW (1977) Excitation-dependent emission in Mg-, Be-, Cd-, and Zn-implanted GaAs. J Appl Phys 48:5043 Yuan HX, Tong FM, Tang DY (1990) Analysis of reverse leakage current mechanisms in Hg1x Cdx Te photodiodes. Chin J Infrared Res 9:415–424 Zanio K (1978) In: Willardson RK, Beer AC (eds) Semicond and semimetals, vol 13. Academic, New York Zheng GZ, Wei YY, Shen JX et al (1994) J Infrared Millimeter Waves 13:347 Ziep O, Genzow D, Mocker M, Herrmann KH (1980) Phys Stat Sol B 99:129

Chapter 3

Recombination

3.1 Recombination Mechanisms and Life Times 3.1.1 Recombination Mechanisms At room temperature, semiconductors can be in a stable equilibrium, but most doped semiconductors or alloys are in metastable states with compositions that are frozen at a temperature where diffusion stops. Under these conditions, the carrier densities of semiconductors are in quasi-equilibrium and remain constant. However, external effects can destroy the balance between thermal excitation and recombination to excite extra carriers. Often the extra carriers that play an important roll in devices are the minority carriers, holes in n-type and electrons in p-type material. If the source of the external effects disappears, the nonequilibrium carrier population will also decrease because the probability of carrier recombination is larger than that of carrier generation. Normally, we call the time duration of the return to equilibrium, the minority carrier life time. As is well known, the carrier life time is very different for different semiconductor materials. For example, it can exceed 102 –103 s for single crystal Ge, and the values can be in the range of 10 s for high-purity Si. However, the carrier life time is quite long, about 102 –103 s or longer for GaAs semiconductor materials. The value is about 1 s for HgCdTe materials. Note that the life time can change over a wide range for different alloy concentrations of the same semiconductor material. HgCdTe infrared detectors are intrinsic photoconductivity or photovoltaic devices. However, the life time of the carriers excited by photons, play an important role in both classes of detectors. The extra carriers can be exited by many methods, such as the photon, X-ray,  -ray, and other particles. In addition, electrical methods also can generate hot extra carriers in the semiconductors. Most often, the extra carriers are generated in the form of electron–hole pairs. But it is also possible to photoexcite donors or acceptors to produce the extra carriers. Once the excitation source is removed, equilibrium will be reestablished.

J. Chu and A. Sher, Device Physics of Narrow Gap Semiconductors, Microdevices, c Springer Science+Business Media, LLC 2010 DOI 10.1007/978-1-4419-1040-0 3, 

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There are three principal recombination mechanisms in semi-conductors: Shockley–Read, Radiative, and Auger recombination. Figure 3.1 shows three recombination mechanisms. Shockley–Read recombination is assisted by a deep energy center in the bandgap. The electrons in the conduction band recombine with the holes in the valance band with the help of the recombination center and the emission of phonons. This recombination mechanism is not intrinsic and can be suppressed by improving the material growth techniques to reduce the number of recombination centers. Radiative recombination is one in which an electron in the conduction band transitions to the valance band to recombine with a hole and emits a photon. It generates a photon with the energy hv, and can be observed in a photoluminescence (PL) measurement. This recombination is intrinsic and is the opposite of photon absorption. Roosbroeck and Shockley (1954) reported the principle mechanism behind radiative recombination in 1954. Auger recombination is shown in Fig. 3.1c. An electron in the conduction band transitions to the valance band to recombine with a hole, and the energy released causes another electron to transition to a higher state in the conduction band or another hole in the valance band to transition to a lower state in the valance band. Finally, the excited electron or hole can relax to their respective band edges and generate a phonon. This is also an intrinsic process and the opposite of a “hot electron (or hole)” process in which an excited electron (or hole) drops into a lower conduction band state (or higher valance band state) and the resulting energy excites an electron–hole pair. The mechanism for a hot electron is shown in Fig. 3.2.

Fig. 3.1 Three recombination mechanisms

Fig. 3.2 The hot electron process

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127

In the beginning, the initial state is a hot electron and the finial state contains two electrons in the conduction band and a hole in the valance band. It is the opposite of Auger recombination. However, for Auger recombination the initial state contains three particles and the finial state contains an electron with a higher energy.

3.1.2 The Continuity Equation and Lifetimes The generation and recombination of carriers can be attributed to both internal and .p/ .p/ external factors. Assuming: gi.n/ ; gi ; ri.n/ ; ri are the generation and recombina.p/ .p/ tion rates of electrons or holes by internal factors, and ge.n/ ; ge ; re.n/ ; re are the generation and recombination rates of electrons or holes by external factors, the continuity equation becomes: 1 @n D  r  Jn C gi.n/ C ge.n/  ri.n/  re.n/ ; @t e

(3.1)

@p 1 .p/ .p/ D  r  Jp C gi C ge.p/  ri  re.p/ : @t e

(3.2)

For an approximation where, ge D re D 0, and if there is no current, J D 0, the above equation simplifies to: @n D gi.n/  ri.n/ : @t Under a steady-state condition,

@n @t

(3.3)

D 0, we have gi.n/ D ri.n/ :

(3.4)

It states that in equilibrium the carrier generation rate is equal to the recombination rate. Let gi and ri in equilibrium be expressed as g0 and r0 . The equilibrium carrier densities for electrons, n0 , and holes, p0 , balance the rates in (3.4). They are responsible for the dark current. In the nonparabolic band approximation, we find: 8 < n0 D Nc e .Ec Ef /=kT : p D Nv e .Ef Ev /=kT : 0 2 .Ec Ev /=kT n0 p 0 D N c N v e D ni

(3.5)

If gi > ri , then @n > 0, and the carrier density increases with time. If the reverse @t is true gi < ri , then @n < 0, and the carrier density decreases with the time. Under @t an adiabatic approximation, there is no current in the semiconductor and no exD gi  ri ¤ 0, governs the relaxation change of energy. The continuity equation, @n @t

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of the excess carriers. If the external factors result in the carrier density increase, nn0 D ın > 0, then the generation rate dominates, ri < gi . If n–n0 D ın < 0, then recombination dominates the relaxation, gi > ri . Define: R D ri  gi

(3.6)

in equilibrium, ri D gi D 0, thus R D 0. If there are excess carriers, then R ¤ 0. Therefore, R reflects the character of the generation/recombination process of the excess carriers in a unit time and volume. The continuity equation with no net current becomes: @n D R.r; t /: (3.7) @t Assuming the recombination probability of the free carriers/unit time and in a unit volume is approximated by 1= n , then R D .n  n0 /= n , (3.7) becomes: @n n  n0 D gi  ; @t

n

(3.8)

 so ın.t / D n.t /  n0 Š gi 1  e t=n . When gi is 0, the deviation from equilibrium vanishes. For finite gi , the deviation relaxes back to equilibrium with a time constant n . However, if initially the system starts in a nonequilibrium state with population n.0/ and relaxes back to equilibrium, then ın D .n.0/  n0 /e t=n . Similarly, (3.8) also applies to holes: p  p0 @p : D gp  @t

p

(3.9)

p is the lifetime of the excess holes in the relaxation time approximation. Note the electron and hole recombination rates need not be the same.

3.1.3 The Principle Recombination Mechanisms and the Resulting Lifetimes of HgCdTe The bulk lifetime of semiconductor materials is mainly determined by recombination. Auger recombination is the dominate mechanism in pure narrow gap HgCdTe materials compared to some wider band gap materials such as GaAs where radiative recombination is also important. Even in wider gap HgCdTe, Auger recombination still plays an important roll. In indirect gap semiconductors like Ge and Si, the Auger process and radiative recombination are complicated by the need for phonon assistance. For the excess carriers in HgCdTe, there are three recombination mechanisms: inter-band direct Auger recombination, inter-band direct radiative recombination, and Shockley–Read recombination assisted by a defect energy level center.

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129

1. Auger recombination (Kinch 1981) Auger recombination mechanisms of types 1 and 7 are the main mechanisms in narrow band materials with a low carrier density (Casselman and Petersen 1980; Casselman 1981). An analytical expression for the recombination time of intrinsic Auger 1 recombination is:      Eg 3=2 m 1=2 2m m0 i 1 C e D 3:8  1018 "21  1 C e

A1 me mh m kB T " # h   1 E m 2m g 1 C e  exp 1 C e (3.10) jF1 F2 j2 : mh mh kB T Here, jF1 F2 j is a product of the Bloch function overlap between the conduction and valance band, and the conduction band edge and an excited conduction band state. Typically, we take jF1 F2 j D 0:20 in order to fit the experimental HgCdTe data for x D 0:2 over a limited temperature range. In fact, when this quantity is calculated using an accurate band structure it turns out that the constant chosen is a poor approximation to its actual k and T dependent behavior for a range of x values (Krishnamurthy et al. 2006). This occurs because band structures, both the gap and wave functions, are temperature dependent. The recombination times of Auger 1 and 7 for HgCdTe have the following form: i z2 =.1 C z2 /;

A1 D 2 A1 i

A7 D 2 A7 z2 =.z C z2 /:

(3.11) (3.12)

Here, z is defined as z p=ni . The ratio of the recombination time for Auger 7and 1 is:

A.7/ m .Eth / .1  5Eg =4kB T / i

D .1/ D2 c  ; (3.13) m0 .1  3Eg =2kB T /

Ai where m0 and mc .Eth / are the effective mass of electrons near the bottom of the conduction band and those at energy Eth , and mhh D 0:5 has been taken. The net Auger lifetime of a nonequilibrium carrier population is A D

A1 A7 =. A1 C A7 /. Figure 3.3 shows the relation between the Auger lifetime and temperature T . Also, Auger 3 and 7 type recombination play an important role in p-type materials. A detailed discussion will follow later in the text. 2. S–R recombination (Pines and Stafsudd 1980) All semiconductor materials have some impurities although they are nearly pure. Some of these impurities have energy levels in the band-gap. These energy levels can assist electron and hole recombination. Therefore, they will increase the recombination probability of a nonequilibrium carrier concentration.

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Fig. 3.3 A relation between the Auger lifetime and temperature T for different carrier concentrations

The S–R recombination lifetime can be calculated using the Shockley–Read equation: n .n0 C n1 C n/ C p .p0 C p1 C p/ ; (3.14)

SR D Nt p n vT .n0 C p0 C p/ which for a small carrier density becomes:       Et EF EF Et kB T kB T n n0 C ni e C p p0 C ni e

S–R D

n p vT Nt .n0 C p0 /

:

(3.15)

Here, p and n are the recombination cross sections of the hole and electron, respectively. The recombination cross sections are in the rangep of 1013 –1017 cm2 , and vT is the thermal speed of electrons in HgCdTe, vT D 3kB T =me . If Nt D 1014 cm3 for HgCdTe with x D 0:2, and suppose Et D Ec  Et D 21 meV and p D n D 1016 cm2 then Fig. 3.4 presents the relation between the S–R recombination lifetime and temperature T . S–R is interdependent of T for low temperatures. In the mid temperature range where expŒ.Eg  Et /=kB T  does not vanish, this recombination mechanism plays an important role. The S–R recombination rate is maximum when Et is close to Ei , and hardly present because of the exponential relation shown in Fig. 3.5. Therefore, only deep energy level impurities affect the lifetime. Equation (3.15) was derived using Boltzmann statistics which is proper for deep levels but not in general. When this type of equation is derived using full Fermi–Dirac statistics, this constraint is removed. Then, the S–R recombination rate is maximized, the life time is minimized, at a temperature when the Fermi level is equal to the trap level even if it is shallow (Krishnamurthy et al. 2006).

3.1 Recombination Mechanisms and Life Times

131

Fig. 3.4 The relation between the R–S recombination lifetime and temperature T

Fig. 3.5 The relation between the R–S recombination lifetime and .Ei  Et /=kB T

3. Radiative recombination (Schacham and Finkman 1985) The lifetime of the inter-band direct recombination can be determined by the Roosbrock–Shockley method: 1 ; B.n0 C p0 C p/  3=2   m0 m0 m0 B D 5:8  1013 "1=2 1 C C 1 me C mh me mh  3=2   300 Eg2 C 3kB TEg C 3:75.kB T /2 : T

R D

(3.16)

(3.17)

132

3 Recombination

Fig. 3.6 The relation between the radiative recombination lifetime and temperature T

Fig. 3.7 The relation between the net lifetime and temperature T

Figure 3.6 shows the relation between the radiative recombination lifetime and temperature T . At low temperature and small carrier density, the lifetime is p interdependent of the temperature and is proportional to exp T  =T with increasing temperature. 4. The bulk radiative recombination lifetime The three recombination mechanisms each have an effect on HgCdTe materials, thus the net lifetime is:   1 1 1 1 C C : (3.18)

D

A

S–R

R If we compare Fig. 3.7 with Fig. 3.3, it is found that the net lifetime is mainly determined by Auger recombination in the low and mid temperature ranges.

3.1 Recombination Mechanisms and Life Times

133

Fig. 3.8 The distribution of lifetimes with composition x at 77K for (a) Nd D 5  1014 cm3 ; (b) Nd D 1  1015 cm3

Figure 3.8 presents the calculated net lifetime. At low temperature, the thermal energy of electrons is very low, and Auger recombination dominates for HgCdTe with alloy compositions x < 0:2 and the doping concentration Nd D 51014 cm3 . The reason is that the band-gap of this material is small and the radiative recombination rate is inversely proportional to Eg2 . However, the Auger intrinsic recombination process rate decreases with an increasing alloy fraction and the subsequent band-gap increases. The radiative recombination rate increases, but in narrow gap material is usually overcome by S–R recombination. Auger recombination plays an important role in HgCdTe with alloy compositions x < 0:23 and the doping concentrations Nd 6 1  1015 cm3 , and S–R recombination, except for very pure material, plays an important role for alloy compositions x > 0:26. At room temperature, the probability of Auger recombination increases because the electron thermal energy increases as seen in Fig. 3.9a, b. The bulk lifetime is mainly determined by Auger recombination. To conclude, Auger recombination is not only special but also the principal recombination mechanism for HgCdTe with low alloy compositions.

134

3 Recombination

Fig. 3.9 The distribution of lifetimes with the composition x at 300 K for (a) Nd D 51014 cm3 ; (b) Nd D 1  1015 cm3

3.2 Auger Recombination 3.2.1 The Types of Auger Recombination Auger recombination can be caused by several different mechanisms consistent with the energy band structure of HgCdTe. Beattie (1962) reported ten possible Auger recombination mechanisms for the conduction band, the heavy-hole band, and the light-hole band. The each of the ten possibilities is consistent with energy and momentum conservation. In each mechanism, the electron transition from the conductive band to recombine with hole in the valance band. The extra energy and momentum is taken up by a second electron or hole transferring to a higher energy state. There are ten possible processes because there is one conduction band and two subvalence bands. Figure 3.10 shows the ten possible processes. Auger recombination mechanism 1 (AM-1) is the main process in the n-type HgCdTe materials because there are many electrons in conduction band and the holes are mainly located in the heavy-hole band. However, AM-3 and AM-7 are the main processes for the p-type HgCdTe materials because there are many heavy

3.2 Auger Recombination

135

Fig. 3.10 Ten possible Auger recombination processes in HgCdTe (Arrows indicate the electron transitions (Beattie 1962))

holes in the valence band and the not many electrons. The other mechanisms are related to the light-hole band and have smaller probabilities compared to the above three processes.

3.2.2 Auger Lifetime The lifetime of the minority carriers is determined by the rate at which carriers generated by an external stimulus relax back to equilibrium. From the electron and hole continuity equations, one can approximate the lifetime: @n 1 n D Œgn  rn  C Uext C r  Jn ; @t e

(3.19a)

@p 1 p D Œgp  rp  C Uext C r  Jp : @t e

(3.19b)

Here, n and p are the concentrations of the electrons and the holes, respectively. gn and gp are the generation rates when there is no external influence, rn and rp are the p n and Uext are the generation rates due to external effects, recombination rates, Uext and Jn and Jp are the drift and diffusion current densities caused by electrons and holes. Equations (3.19a) and (3.19b) are the basic formalisms for a current calculation in a p–n junction (Blakemore 1962; Many et al. 1965). Let (3.20) n D n0 C rn and p D p0 C rp;

(3.21)

136

3 Recombination

where n0 and p0 are the equilibrium electron and hole densities and rn and rp are the deviation from these densities due to extrinsic effects. In the relaxation time approximation, we have for electrons: rin D 

n0 C rn :

n

(3.22)

Now, let the current densities and extrinsic generation and recombination terms vanD @p D 0, and rn D rp D 0, we find for ish. Then, in equilibrium where @n @t @t electrons: n0 D gn n : (3.23) The continuity equation for electrons now simplifies to: @rn 1 rn n D r  Jn C Uext  : @t e

n

(3.24)

A similar treatment applies to holes, so the hole continuity equation is: @rp 1 rp p D r  Jp C Uext  : @t e

p

(3.25)

If the divergence of the current density r  Jn is zero, then the continuity equation simplifies to: n @n n  : (3.26) D Uext @t

n If the relaxation lifetime n is independent of time then the solution to (3.26) for n is an exponentially decreasing function. Generally speaking, n and p depend on the carrier concentrations. However, (3.26) is still effective. For an Auger process: n  n0 ; (3.27)

n;A D .rn;A  gn / here n0 is the equilibrium carrier concentration. Subscript A denotes an Auger processes. Equation (3.26) can be derived from the transition and recombination probability of an electron and a hole per unit volume and including Fermi–Dirac statistics. In the parabolic approximation for the bands: 8 < g .1/ D

n .1/ g n0 0

: r .1/ D

n2 p .1/ r0 n2 0 p0

:

(3.28)

Here, superscript 1 indicates an AM-1 process. The generation rate must be equal to the recombination rate in the steady state. If we have n D p, then:

A.1/ D

n4i 1 : np0 .n C p0 / g .1/ 0

(3.29)

3.2 Auger Recombination

137

The above equation indicates that the Auger lifetime A.1/ can be determined when g0.1/ is known. Considering an integral over the transition probabilities per unit time for all electrons, the generation rate in the absence of an external excitation mechanism, can be calculated. The transition probability from an initial to a final state during the time period t is reported by Schiff (1955): Tif D

1  cos x 2t 2 ; jUif j2 2 „ x2

(3.30)

Here, x D .t =„/ jEf  Ei j, Ei and Ef are, respectively, the initial and final states energies. Uif is the interaction matrix element. The appropriate wave functions are the products of space functions and spin–orbit functions S;T : ˇ ˇ E D  ˇ .1/ ˇ jUif j D 'S;T ˇH ˇ S;T ;

(3.31)

H .1/ is a two electron state interaction perturbation: H .1/ .r1 ; r2 / D

e 2 exp. jr1  r2 j/ : " jr1  r2 j

(3.32)

 is the screening length and " is the dielectric constant. Thus, we find: g0.1/ D

  V 4 1 t v 8 3 ZZZZ

  Tif Œf .k1 / Œf .k2 / 1  f .k10 / 1  f .k20 / dk1 dk2 dk10 dk20 : 

(3.33) The detailed calculation can be found in a paper by Beattie and Landsberg (1959) and another review by Petersen (1970). If the screening effect is neglected and under the parabolic nongenerate band approximation we find: g0.1/ D

8.2/5=2 e 4 m0 .m0 =m0 / jF1 F2 j2 n0 h3 "2 .1 C /1=2 Œ1 C 2



kB T Eg

3=2 e

h   E i g  1C2 1C k T B

:

(3.34) jF1 F2 j is the product of the overlap integrals between the bottom of the conduction band and the valence band and the bottom of the conduction band and an excited conduction band state with energy Ee Š Eg . This product is approximated by a constant lying in the range 0:20  0:25.  is the ratio of the electron effective mass in the conductive band to the effective heavy hole effective mass in the valence band. Equation (3.34) can be used to calculate the Auger 1 (AM-1) recombination rate. Then, one can calculate the carrier lifetime for n-type HgCdTe from (3.29). One simplified equation form for A.1/ can be written as (3.28).

138

3 Recombination

If the contribution from the light hole is neglected, the Auger recombination 3 (AM-3) in p-type HgCdTe can be expressed as: g0.3/ D

.mhh =m0 / jF1 F2 j2 8.2/5=2 e 4 m0 p0 h3 "2 .1 C 1=/1=2 Œ1 C 2=



kT Eg

3=2 e

h  E i g  2C 1C kT

:

(3.35) Then, the generation and recombination determined by AM-3 is: g .3/ D

p .3/ .3/ p2n g0 ; r D 2 r0.3/ : p0 p 0 n0

(3.36)

Thus, one can calculate the total lifetime due to the combination of AM-1 and AM-3 determined from (3.36) to be:

A D

D

n4  i  .n0 C p0 C n/ g0.1/ p0 n C g0.3/ p0 n h i 2n2i n0 =2g0.1/ .n0 C p0 C n/Œ.n0 C n/ C ˇ.p0 C n/

:

(3.37)

Here, n D p has been assumed. The parameter ˇ is: ˇD

n0 g0.3/ p0 g0.1/

    1   Eg 1=2 .1 C 2/ exp  : D 2C 1 C  kB T

(3.38)

Equation (3.37) enables a study of the relations among the Auger lifetime temperature and carrier concentration. For the lifetime of intrinsic HgCdTe materials,   1 and the lifetime from (3.37) or (3.29) yields a relation:

Ai D

ni 2g0.1/

D

n0 2g0.1/

:

(3.39)

Then, the lifetime A can be expressed in terms of the function Ai . For n-type materials with n  n0 , and n0  ˇp0 :

A Š 2

  n2i 1  Eg :

/ exp Ai 1 C  kB T n20 n20

Thus, we find: 2n2i Ai



 Eg / exp 1 C  kB T

(3.40)

 :

(3.41)

From the above form, one can conclude that the Auger lifetime depends on the bandgap energy with which it has an exponential relationship. When the effective mass fraction, , and the band-gap decreases the carrier lifetime also decreases.

3.2 Auger Recombination

139

Fig. 3.11 The intrinsic Auger lifetime depends on the temperature for different alloy fractions of HgCdTe material with jF1 F2 j D 0:25

For p-type materials, ˇp0  n0 we have:

A D

  2 n2i 1  Eg :

/ exp Ai ˇ p02 1 C  kB T ˇp02

(3.42)

Comparing (3.40) with (3.42), the carrier lifetime of a p-type material is longer than that of an n-type material due to ˇ  1 for the same carrier concentration. In addition, one can calculate the Auger lifetime of p-type or n-type materials if the parameters, ˇ; Ai and the carrier concentrations are known. For an intrinsic Auger lifetime Ai D ni =2g0.1/ ; g0.1/ can be calculated from (3.35). Figure 3.11 shows that the intrinsic Auger lifetime depends on the temperature for different compositional fractions, x, in Hg1x Cdx Te because the band-gap and wave functions vary with x. Because of this fact taking a constant, jF1 F2 j D 0:25, is only an approximation (Krishnamurthy et al. 2006). The relationship between parameter ˇ and the HgCdTe alloy composition fraction x at different temperatures is shown in Fig. 3.12. Evidently ˇ  1 is found for most situations. Note that the above calculation contains the following approximations: a two-band model, neglecting the light hole and spin–orbit bands, taking parabolic bands, letting jF1 F2 j be a constant, and assuming nongenerate distributions. For n-type HgCdTe materials with low concentrations, the above approximations are reasonable and the theoretical calculations are in agreement with the experimental results. However, for p-type HgCdTe materials, the agreement is not good and the lifetime decreases when account is taken of the light-hole band. If we consider the effect of a nonparabolic band and the jF1 F2 j dependence on k, and ˇ  1 then the Auger lifetime for n-type HgCdTe materials can be calculated. Equation (3.37) can be simplified to:

A D

2n2i n0 =2g0.1/ : .n0 C p0 C n/.n0 C n/

(3.43)

140

3 Recombination

Fig. 3.12 The relationship between the parameter ˇ and HgCdTe alloy fraction at different temperatures

g0.1/ has been obtained under the above generalized conditions by Petersen (1970) and the results indicate that A0 is the same as A for temperatures between 100 and 300 K derived with none above effects included. However, A0 is shorter than A between 77 and 100 K (x D 0:2, and ND D 1014 cm3 ). Evidently, (3.43) can be used to approximate the Auger lifetimes of n-type HgCdTe materials. In (3.34) and (3.35), the exponential terms in g0.1/ and g0.3/ take the following forms:     1 C 2 Eg .1/ ; (3.44a) g0 / exp  1 C  kB T and

    2 C  Eg g0.3/ / exp  : 1 C  kB T

(3.44b)

For an AM-1 process, define: Eth1 



 1 C 2 Eg : 1C

(3.45a)

 2C Eg : 1C

(3.45b)

For an AM-3 process, define: Eth3 



Eth are the threshold energies for these processes. These relationships can be derived from energy and momentum conversation in their respective Auger recombination

3.2 Auger Recombination

141

processes. The physical meaning of Eth is that it is the minimum energy required for an electron/hole recombination to occur via an Auger AM-1 or AM-3 process. Because  D me =mhh  1; Eth1 Š Eg , so the AM-1 recombination rate can be simplified to:   Eg : (3.46) g0.1/ / exp  kB T Similarly, we find Eth.3/ Š 2Eg for an AM-3 process; Eth.2/ Š  2Cm e =mhh    2Cme =mhh m lh =mhh

 1C2m e =mlh  Eg 1Cm e =mlh

Š 32 Eg

for an AM-2 process; and Eth.7/ Š Eg Š Eg for an AM-7 process. From (3.46), the steady-state population is proportional to an exponential of the threshold energy. Therefore, in n-type material, if Eth > Eg in an Auger process AM-3 is playing a role, while if Eth Eg Auger MA-1 dominates. Moreover, in p-type, Auger 1 and 7 will dominate because the heavy-hole band plays an important role because the state density of the light-hole bands is less than that of the heavyhole bands. The Auger 3 process is also very important in heavily doped p-type materials. For an AM-7 process, the recombination between an electron in the conductive band and a hole in the heavy-hole band is assisted by exciting an electron in lighthole band into the heavy-hole band. By considering nonparabolic bands, the jF1 F2 j dependence on k, and nongenerate statistics, Beattie and Smith (1967) deduced the relation:   3=2 plh n0 1 th 2n0 phh .7/  ; (3.47)

A D D.Eth / 1 C p0;hh n np0;lh I.th / where th D Eth =kT , and D.Eth / is a function of the effective mass, jF1 F2 j, and threshold Eth . I.th / is an integral over the conduction band. Assuming the same Fermi level holds for the light- and heavy-hole bands, and the effective mass are constants, (3.47) can be simplified as:

A.7/ D

.7/ 2n2i Ai n0 =p0 .7/  2 Ai D ; 1 C n0 =p0 .n0 C p0 /p0

(3.48)

.7/ is the intrinsic lifetime for AM-7. For intrinsic materials, the bracketed where Ai item in (3.47) is 1/2, thus: 3=2

.7/ D

Ai

D.Eth / th : 2 I.th /

(3.49)

For an AM-1 process, A.1/ is given by (3.37) and (3.40), and the intrinsic limit by (3.39). When n is very small:

A.1/ D

.1/ 2n2i Ai 1 .1/  2 Ai D : 1 C n0 =p0 .n0 C p0 /n0

(3.50)

142

3 Recombination

.7/ .1/ Thus, one can compare Ai with Ai , from (3.48) and (3.50), we find:

A.7/

A.1/

D

.7/ .7/ n2i Ai n0 Ai D : .1/ p0 .1/ p02 Ai Ai

(3.51)

Casselman and Petersen (1980) calculated the results: D

.7/

Ai .1/

Ai

 mc .Eth / 1  54 th

; D2 m0 1  32 th

(3.52)

where mc .Eth / is the effective mass of the conduction band at Eth , and m0 is the effective mass at the conduction band edge. Eth.1/ Š Eth.7/ D Eg , for the alloy concentrations, 0:16 < x < 0:3, temperatures 50 K < T < 100 K, and 0:1 <  < 6 (Casselman and Petersen 1980). So, one can conclude that AM-1 and AM-7 processes play important roles in both n-type and p-type materials. Similarly, we can compare AM-7 with AM-3, which are important in p-type semiconductors:

A.7/

A.3/

1 D 2



m0 mhh



  Eg : exp  kB T

(3.53)

The  value and the other band parameters must be assigned to complete the above expression. Note that the above discussion is only valid for a nondegenerate population distribution. Degeneracy can always exist in a small fraction of a HgCdTe material or at low temperatures even for x D 0:2 samples. In a case where the band-gap is small and the electron effective mass in the conduction band is also very small, then the Fermi level lies above the conduction band edge. In such cases, the Auger process is modified. Other abnormal cases occur, at low temperature when a local concentration fluctuation causes the band-gap and the effective mass in the conduction band to be very small, or if there is a local carrier concentration fluctuation to a higher value. Then, space charge layers are formed causing the bands to bend so that the Fermi level lies above the conduction band edge. In such local regions, the Auger process is modified. Therefore for an AM-1 process, the electrons from the Fermi level transition from above the bottom of conduction band to the valence band to recombine with holes and the extra energy excites electrons from the Fermi level to the higher energy states. The detailed process is shown in Fig. 3.13. For a degenerate case, Gerhardts et al. (1978) investigated the Auger lifetime of n-type HgCdTe and found: Z Z e 4 m0 4 5 2 1 0 3 .2  " N / .1 C p=k T n /E k d d3 k2 v B f 1 „3 f .E1 /f .E2 /Œ1  f .E10 / exp.E20 =kB T /M k10 .E10  Eg /=Ep : (3.54)

1 D 3

3.2 Auger Recombination

143

Fig. 3.13 An AM-1 transition processing in a degenerate case

Fig. 3.14 The relation between the carrier lifetime and temperature for an n-type Hg0:2 Cd0:8 Te sample with different carrier concentrations

Here, Nv is the effective valence band state density. n0 D dn=dE1 ;  D .EE  Ec /kB T , and M is a transition matrix element. The calculated results are given by the dashed curves in Fig. 3.14. The dots are the  1=T experimental data for the different carrier concentrations.

144

3 Recombination

3.3 Shockley–Read Recombination 3.3.1 Single-Level Recombination Center Shockley–Read is a basic process for electron–hole recombination in a semiconductor, there are several classic text books dealing with the mechanism (Shockley and Read 1952; Hall 1952; Sah and Tasch 1967; Milnes 1973). Nonequilibrium electrons (holes) created by an external excitation in intrinsic semiconductors rapidly relax to the bottom (top) of conduction (valence) band and then recombine with holes (electrons) within a characteristic lifetime. If there are impurity-related energy levels in the band-gap, the recombination rate will be enhanced, and thus the carrier lifetime is shortened. As shown in Sect. 3.1, starting from a nonequilibrium distribution, no external excitation source, and in the relaxation time approximation we find: (3.55) n D n0 exp.t = n / C n0 and



p D p0 exp t = p C p0 :

(3.56)

Now, we consider the trap capture cross-section and occupation probability. According to the model proposed by Shockley–Read (Shockley and Read 1952), who studied carrier dynamics at a single energy level within the band-gap, there are four possible processes involving the deep energy center as shown in Fig. 3.15. (a) An unoccupied neutral deep center, with a concentration of NT0 , captures one electron from the conduction band, with a capture cross-section or recombination cross-section n , and a capture rate (i.e., capture coefficient or recombination rate) cn D n vn , where vn is the thermal speed of the electrons. NT0 C e ! NT :

(3.57)

(b) An occupied deep center emits electrons onto the conduction band with an emission rate en . (c) A hole is captured by an occupied center with a capture cross section p and a capture rate cp D p vp , where vp is the hole thermal speed. NT C h ! NT0 : (d) A hole is emitted from an unoccupied center with an emission rate ep .

Fig. 3.15 Four possible capture and emission processes for electrons and holes

(3.58)

3.3 Shockley–Read Recombination

145

The capture rate of an electron is proportional to the electron’s concentration n at bottom of conduction band and the unoccupied deep center concentration NT .1  fT /, where fT is the Fermi–Dirac distribution function. If ın is small, then fT is the equilibrium value of its distribution function, i.e.:    ET  EF 1 fT D 1 C exp : kT

(3.59)

If ET  EF  kT , (3.59) simplifies to its Maxwell–Boltzmann form: fTMB

   ET  EF 1 D exp : kT

(3.60)

Obviously in the absence of an external generation mechanism, the electron emission process (b) depends on the rate en and the fraction of the occupied center concentration NT fT . In the general case, if ın is small, EF is not changing, and the Fermi–Dirac distribution function fT is only a function of temperature T , it does not depend on time t . So, the electron concentration changes as: dn.t / D cn n .t / NT .1  fT / C en NT fT : dt

(3.61a)

Similarly, for holes the change is dp .t / D cp p .t / NT fT C ep NT .1  fT /: dt

(3.61b)

However, if in the critical theoretical consideration, any change of electron density ın in the conduction band, it must be related to the change of Fermi level EF , then the Fermi–Dirac distribution function fT is not only a function of temperature T but also a function of time t . In this case, the situation becomes complicated, (3.61a) and (3.61b) become: dn.t / D cn n .t / NT .1  f .t // C en NT f .t /; dt

(3.62a)

and

dp .t / D cp p .t / NT f .t / C ep NT .1  f .t //: (3.62b) dt Equations (3.62a) and (3.62b) constitute two equations in three unknowns, n .t /, p .t /, and f .t /. The third equation is charge neutrality: n.t / C NT f .t / D p .t / :

(3.62c)

These equations constitute to a nonlinear set of first-order differential equations.

146

3 Recombination

Under steady-conditions equilibrium (dn=dt D 0; dp=dt D 0; n D n0 , and p D p0 ), we obtain from (3.61a):   ene ET  EF

n1 ; D n0 exp (3.63) cne kT rate and the capture rate at equilibrium. In fact, n1 where ene and cne are   the emission Ec ET , which is the electron concentration when the Fermi is equal to Nc exp kT level overlaps with the impurity level ET . Similarly, from (3.61b), we obtain:   epe EF  E T

p1 : D p0 exp (3.64) cpe kT We can also rewrite (3.61a) and (3.61b) into: dn D cn .nNT0  n1 NT / dt

(3.65)

and

dp D cp .pNT  p1 NT0 /; (3.66) dt where the capture trapping center for an n-type material is in one of the two timedependent acceptor states, NT or NT0 . For a p-type material, there is a larger chance if it can do so, the trap will first capture a hole to become NTC and then capture an electron to assist the recombination. But here we assume the trap is such that it has only one empty state that can accommodate an electron but not a hole. Then, NT0 D NT .1  f /; NT D NT f , and NT0 C NT D NT , where NT is the total density of traps. Obviously, the rate at which NT traps are formed is: dn dp dNT D C D cn .nNT0  n1 NT /  cp .pNT  p1 NT0 /: dt dt dt

(3.67)

When all the trap centers are neutral, the maximum rate at which neutral traps are formed is the minimum recombination lifetime and it is:

n0 D

n 1 D D .n vn NT /1 : dn=dt jN 0 !NT cn N T

(3.68)

T

Similarly, when NT ! NT , the minimum possible lifetime of holes is:

p0 D

1

1 D p vp NT : cp N T

(3.69)

The results of (3.68) and (3.69) can be also obtained from an analysis in which the trap population is assumed to remain nearly constant in a Fermi distribution as the system relaxes from an initial nonequilibrium to its equilibrium distribution. See Appendix 3.A.

3.3 Shockley–Read Recombination

147

In the case of equilibrium, it means there are no electrons captured or emitted by dN  capture centers, i.e. dtT D 0, and we obtain NT from (3.67):

So, NTo is:

c n n 0 C cp p 1 NT : D NT cn .n0 C n1 / C cp .p0 C p1 /

(3.70)

c n n 1 C cp p 0 NT0 : D NT cn .n0 C n1 / C cp .p0 C p1 /

(3.71)

At this point, the Shockley–Read treatment makes an unjustified approximation. They say there is a steady-state established darning the entire time the system is returning to equilibrium, so in (3.70) and (3.71), n0 and p0 can be replaced by n.t / and p.t /. Given this approximation and substituting NT from (3.70) and NT0 from (3.71) into (3.65) and (3.66), we obtain: np  n2i dn dp D D : dt dt

p0 .n C n1 / C n0 .p C p1 /

(3.72)

D dp , is treated as a consequence derived from the “steadyIn this equation, dn dt dt state” approximation but it could just as well be taken as the “steady-state” approximation. In that case, f .t / is solved in terms of n.t / and p.t / from the condition dn D dp and substituted into either (3.61) or (3.62) to obtain (3.72). Once again dt dt there is no justification for this approximation other than it makes the expressions more tractable. The proper way to proceed is to use the two continuity equations and the charge neutrality condition as the third equation to solve the three unknowns n.t /, p.t /, and f .t /. Since many deep centers act as acceptors, we now discuss the effects on an n-type semiconductor with acceptor centers. Under external perturbations such as photon excitation or charge injection, the density of electrons (holes) increases from its equilibrium value n0 .p0 / to n0 C n0 .p0 C p0 /. As soon as the external perturbation stops, the density of electrons and holes begin to decrease toward their equilibrium values again by following the equation: .n0 C n0 /.p0 C p0 /  n2i dp dn D D : dt dt

p0 .n0 C no C n1 / C n0 .p0 C po C p1 /

(3.73)

According to: dn n D ; dt

n

(3.74)

p0 .n0 C n0 C n1 / C n0 .p0 C p0 C p1 /  n0 : .n0 C n0 /.p0 C p0 /  n2i

(3.75)

we have:

n D 

148

3 Recombination

1

Substituting p0 D p vp NT and n0 D .n vn NT /1 into (3.75), we obtain:

n D 

n vn .n0 C n0 C n1 / C p vp .p0 C p0 C p1 /

  n0 : n p vn vp NT2 .n0 C n0 /.p0 C p0 /  n2i

(3.76)

D  p and the fact that An identical expression for p can be obtained from dp dt p in this case rn0 D rp0 . Thus, the S–R lifetime can be expressed in a single formula by letting n D S–R . Neglecting n0 and p0 when they are small, (3.76) becomes:

S–R D

p0 .n0 C n1 / C n0 .p0 C p1 / n 0 C n1 p 0 C p1 D p0 C n0 : .n0 C p0 / n0 C p0 n0 C p0

(3.77)

As an example, examine a case of a Au doped n-type Si, in which the concentration of electrons is 1016 cm3 and the density of Au atoms is 5  1015 cm3 . The resistance of this Si is 1  cm at 300 K. Supposing all Au atoms in Si are in the form of Au and form a deep level at Ec  0:54 eV; the observed capture cross-sections p Š 1015 cm2 and n Š 5  1016 cm2 for the processes are Au C h ! Au and Au C e ! Au , respectively; and the thermal velocity of electrons vn is of order of magnitude of 107 cm=s and that of the holes vp Š 106 cm=s, then we obtain: 1

p0 D p vn NT D .1015  107  5  1015 /1 D 2  108 s; (3.78) 1

16 6 15 1 7

n0 D n vp NT D .5  10  10  5  10 / D 4  10 s; (3.79) from (3.68) and (3.69). Note that n1  p1 =50  2  1010 cm3 but even though p1  50p0 , it can still be neglected with respect to n0 .1016 cm3 /. This is a case where the Fermi level lies well above the trap level, so n0 approximates S–R . So, the Au in Si is effective in decreasing the minority carrier lifetime for a high sensitivity device. In p-type Si, the donor deep level at Ev C 0:35 eV formed by Au plays a same role as Au in n-type Si.

3.3.2 General Lifetime Analysis The prerequisites for the discussion in last section are, n0 D p0 ; zero external generation, a low density of recombination centers; and single-trap energy level. In a more general case, i.e. without these simplifications, the expressions in last section will be more complicated. In the case of n0 ¤ p0 , which occurs when there is a low injection density, the lifetime derived by Shockley (1958) is: 

n0 .p0 C p1 / C p0 Œn0 C n1 C NT .1 C n0 =n1 /1 

p D n0 C p0 C NT .1 C n0 =n1 /1 .1 C n1 =n0 /1

 (3.80) n!0

3.3 Shockley–Read Recombination

149

and 

p0 .n0 C n1 / C n0 Œp0 C p1 C NT .1 C p0 =p1 /1 

n D n0 C p0 C NT .1 C p0 =p1 /1 .1 C p1 =p0 /1

 :

(3.81)

p!0

If NT is small, (3.80) and (3.81) reduce to a single expression:

0 D

p0 .n0 C n1 / C n0 .p0 C p1 / : n0 C p0

(3.82)

In the case of a high carrier concentration, Shockley and Read (1952) derived the following expression: 

D 0

 1 C n0 . n0 C p0 /=Πp0 .n0 C n1 / C n0 .p0 C p1 / ; 1 C n0 =.n0 C p0 /

(3.83)

where 0 is given in (3.82), indicating the lifetime varies starting from 0 as n0 increases. For heavily doped n-type samples (3.83) can be expressed in terms of the change of conductivity  and the ratio b of the electron mobility to the hole mobility: "

Š 0 

Š 0 where ı D

1C

b Œ. p0 C n0 /= p0  0 .1Cb/ 1 C 0b .1Cb/

# or

 1 C ıŒ. p0 C n0 /= p0  ; 1Cı

(3.84) (3.85)

b . 0 .1Cb/

Sandiford (1957) analyzed the role of Shockley–Read–Hall-type centers in the transient photoconductivity decay assuming that the trap populations are time independent. He combined (3.65) and (3.66), and found an expression: p D Ae t=C C Be t= ;

(3.86)

where A and B are determined from the initial conditions. He treats a case (see Appendix 3.B) where the deviation from equilibrium are small, so f .t / can be approximated by fT (NT and NT0 are constants), and NT is small enough so the following approximation holds: Œcp .NT C p0 C p1 / C cn .NT0 C n0 C n1 /2 >> 4cp cn ŒNT NT0 C NT .n0 C n1 / CNT0 .p0 C p1 /:

(3.87)

Following this logic, he finds: i h i1  h

C D cp p0 C p1 C NT .1 C p0 =p1 /1 C cn n0 C n1 C NT .1 C p0 =p1 /1 (3.88)

150

3 Recombination

and

 D

   

n0 p0 C p1 C NT .1 C p0 =p1 /1 C p0 n0 C n1 C NT .1 C n0 =n1 /1 n0 C p0 C NT .1 C n0 =n1 /1 .1 C n1 =n0 /1

(3.89)

Hence, the decay of p or n may not be expressed by a single exponential. In some circumstance, there is a big difference between C and  . For instance, when cp D 109 cm3  s1 ; cn D 107 cm3 s1 ; NT D 1013 cm3 ; n0 D 1014 cm3 , and p1 D 3  1016 cm3 , he obtains C D 400s and  D 0:025s. However, as shown in Appendix 3.B, in the case of an n-type semiconductor, A Š 0 and B Š p.0/, one cannot conclude that the fast decay dominates. There are other cases where A > B, so there is a fast decay with amplitude A followed by a slower decay with amplitude B. In still other cases, A > 0, is positive while, B < 0, is negative so there is an overshoot of the decay. Wertheim (1958) studied transient recombination. He got the same expression as those in (3.88) and (3.89), but expressed them in a different form: 1

;

i D cp Œp0 C p1 C NT  C cn Œn0 C n1 C NT 

t D

n0 .p0 C p1 C NT / C p0 .n0 C n1 C NT / n0 C p0 C .NT NT0 =NT /

(3.90) (3.91)

Figure 3.16 shows the relation of lifetime and temperature for a surface bombarded n-Si. An energy level is produced at 0.27 eV above the valence band, which acts as a recombination center. The density of these centers can be created controllably. In this case, an expression (3.92) was obtained by Wertheim when condition (3.87) is satisfied.

t D

1 1 C p1 =NT C : cp N T cn n0

(3.92)

Equation (3.92) indicates as the density of bombarding electrons increases to produce NT , the lifetime reaches a minimum. But actually in Fig. 3.16a, a minimum is observed at 1017 cm2 which is hard to interpret since n0 is not a constant and decreases during bombardment. Equation (3.92) describes the lifetime variations under various bombardment conditions. The other issues Wertheim dealt with include (a) direct recombination and recombination via trap centers; (b) recombination in crystals with two recombination centers. For the late case, if N1 C N2 < n0 C p0 , he obtained: 1 Œ.1 C 1 /= 1  C Œ.1 C 2 /= 2  D :

1 C 1 .1 C v1 / C 2 .1 C v2 /

(3.93)

3.3 Shockley–Read Recombination

151

Fig. 3.16 The electron lifetime of an electron bombarded n-Si (7 cm) in which an acceptor level is produced at Ev C 0:27 eV. (a) The curve relating the lifetime to n, the density of electrons bombarding the sample. (b) The curves relating the electron lifetime and to the temperature under three bombardment conditions

In an n-type material, the quantities in this expression are defined as follows: 1 D N1 =Œp0 C p11 C .n0 C n11 /cn1 =cp1 ; 2 D N2 =Œp0 C p12 C .n0 C n12 /cn2 =cp2 ; v1 D cn1 .n0 C n11 /=Œcn2 .n0 C n12 / C cp2 .p0 C p12 /; v2 D cn2 .n0 C n12 /=Œcn1 .n0 C n11 / C cp1 .p0 C p11 /;

(3.94)

where n11 ; p11 are the concentrations of electrons and holes, respectively, when the Fermi level is located at the first impurity level. The n12 and p12 are the corresponding quantities related to the second impurity. From (3.89) and (3.90), in general the reciprocal of the time constants are matched when I  1 and i vi  1, and only when the density of recombination centers is low enough. c N When the recombination centers’ levels are close to mid-gap, cpini ni0 < 1; i D 1; 2 is required, indicating a deviation will happen if one of the two centers is negatively charged since cp > cn is possible. Choo (1970) studied the carrier lifetimes in semiconductors containing two recombination energy levels with and without interactions between them. Baicker and Fang (1972) theoretically studied two single-valence trap centers, or one set of valence two trap centers in silicon. Similar issues were considered by Srour and

152

3 Recombination

Curtis (1972) in studying impurities introduced by radiation. These analyses offer a reference in a study of the carrier lifetimes in narrow semiconductors in which the impurities are produced by high-energy radiation.

3.4 Radiative Recombination 3.4.1 Radiative Recombination Processes in Semiconductors Investigations into radiative recombination are very important to semi-conductor physics and to luminescent devices such as LEDs and lasers. The excess carriers created by electron excitation, current injection, or optical pumping relax back to their equilibrium state driven by different recombination mechanisms. In an intrinsic semiconductor with a direct band-gap, an electron and a hole recombine radiatively to emit a photon, as shown in Fig. 3.17. The photon emission spectrum depends on carrier distributions in the conduction and valence bands and the momentum conservation law. The momentum conservation law requires a near identical electron and hole momentum because the momentum of photon is much smaller than that of the electrons and holes. Supposing the transition matrix elements are constants with respect to energy, the emission intensity (Mooradian and Fan 1966) per unit photon energy, under a parabolic approximation, is: (3.95) I.h / / 2 .h  Eg /fe fh ; where h is the photon energy, and fe and fh are Fermi distribution functions of electrons and holes, respectively. If electrons and holes obey a Maxwell–Boltzmann distribution, then: I.h / / 2 .h  Eg / expŒ.h  Eg /=kB T ;

(3.96)

where the Coulomb interaction among the free electrons and between the free electrons and holes are not included. At low temperature and low excitation density

Fig. 3.17 Diagram of radiative recombination

3.4 Radiative Recombination

153

the recombination happens starting from exciton states or bounded impurity states rather than band-to-band transitions since the free carriers may quickly relax to free exciton or be bound at impurity sites. At high temperature (i.e. kB T > E 0 , with E 0 related to a bound state energy), then band-to-band transitions will dominate the recombination process because the bound carriers thermally disassociated to free states near the band edges. The PL of the narrow direct band-gap semiconductor HgCdTe is discussed in Sect. 3.6. For a PL study of InSb, the reader is referred to the early work done by Mooradian and Fan (1966). The recombination rate of free carriers is proportional to square of the carrier concentration n and a factor B; n2 B, where B depends on the transition matrix elements. The factor B can be obtained from the above expressions under an equilibrium condition, where the recombination rate is equal to absorption rate.

3.4.2 Lifetime of Radiative Recombination The radiative recombination lifetime is expressed as 1= D nB. The lifetime is inversely proportional to the carrier concentration. For GaAs, B D 109 cm3 s1 , and when n is less than 1016 cm3 , the band-to-band radiative recombination lifetime is about 107 s. For such long radiative lifetimes, the shorter nonradiative lifetime will dominate the recombination processes. In the case of indirect band-gap semiconductors, phonons in a second-order process must be involved in the recombination process in order to conserve momentum, as shown in Fig. 3.18. In this case, the recombination rate is quite slow. Various possible radiative recombination processes are shown in Fig. 3.19. In thermal equilibrium, the recombination rate of electrons and holes is equal to the photon-induced generation rate. The recombination rate is proportional to the square of intrinsic carrier concentration: GR D Bn2i ;

Fig. 3.18 Diagram of an indirect recombination process

(3.97)

154

3 Recombination

Fig. 3.19 Various possible radiative recombination processes

while the generation rate equals the photon absorption rate at temperature T , (Roosbroeck and Shockley 1954). Thus, we have: GR D

8 h3 c 2

Z

1

0

".E/˛.E/E 2 dE : exp.E=kB T /  1

(3.98)

where GR is radiative recombination rate at thermal equilibrium, ".E/ is the relative dielectric constant, and ˛.E/ is the absorption coefficient. The coefficient B is: BD

1 8 n2i h3 c 2

Z

1

0

".E/˛.E/E 2 dE : exp.E=kB T /  1

(3.99)

B has dimensions cm3 :s1 , GR has dimensions cm3 :s1 , and the right side of (3.98) also has dimensions cm3 :s1 . At thermal equilibrium, a balance between creation and recombination of an electron–hole pair is required, i.e. n0 D p0 D ni for an intrinsic semiconductor, where n0 and p0 are thermal equilibrium concentrations of electrons and holes, respectively. When semiconductors are excited externally, excess carriers are created, and thus recombination is a dominant process leading to an equilibrium state. In this case, the recombination rate of the excess carriers becomes (Tang 1974): (3.100) R D B.np  n2i /: In the case of weak excitation, n D n0 C n, p D p0 C n, n << n0 ; p0 , then the radiative lifetime is:

n D p D R D

n n : D R B.np  n2i /

(3.101)

We have

R D

1 1  : B.n0 C p0 C n/ B.n0 C p0 /

(3.102)

Substituting (3.97) into (3.102), we have:

R D

n2i n2i  GR .n0 C p0 C n/ GR .n0 C p0 /

(3.103)

3.4 Radiative Recombination

155

GR is determined by (8.105) and for intrinsic materials n0 D p0 D ni , we find: 1 : 2Bni

(3.104)

2 Ri ni : n0 C p0

(3.105)

Ri D Substituting B into (3.102), we obtain:

R D

For n-type semiconductors, n0  p0 , then: 1 D 2 Ri

R D Bn0



ni n0

 :

(3.106)

:

(3.107)

For p-type semiconductors, p0  n0 , then:

R D

1 D 2 Ri Bp0



ni p0



From (3.101) and (3.102), the radiative recombination lifetime is inversely proportional to the majority carrier concentration. In (3.104), (3.106), and (3.107), the lifetimes are related to the coefficient B, which can be calculated from (3.99) after substituting the absorption spectrum and the dielectric response into it. The absorption spectrum and dielectric response has been discussed in detail in Chap. 4 of “Physics and Properties of Narrow Gap Semiconductors” (Chu and Sher 2007). Using an expression of Bardeen et al. (1956), Schacham and Finkman (1985) derived an expression for absorption coefficient: 22=3 m0 q 2 ˛ D 1=2 2 „ 3"



me mh m0 .me C mh /

3=2 

m0 m0 1C  C  me mh



E  Eg m0 c 2

1=2 : (3.108)

If Eg > kT , then   3=2   m0 m0 300 3=2 m0 1 C C B D 5:8  1013 "1=2 me C mh me mh T   Eg2 C 3kB TEg C 3:75k 2 T 2 (3.109) or !3=2   me mh 1 m0 m0 28 1=2

 B D 2 8:685  10 " 1 C  C  .kT /3=2 : me mh ni me C mh m0    Eg Eg2 C 3kB TEg C 3:75k 2 T 2 (3.110)  exp  kT

156

3 Recombination

Considering the electrons that are involved in the recombination process are distributed at the bottom of the conduction band, substituting ˛.E/ in (3.99), Schacham et al. obtained a simplified expression: BD

   Eg  2 1 17 3=2 Eg C 3kB TEg C 3:75kB2 T 2 ; (3.111) 2:8  10 "ˇT exp  2 kT ni

where 5

ˇ D 2:109  10



1Cx 81:9 C T

1=2

.cm1 eV1=2 /:

(3.112)

The parabolic approximation used to derive (3.108) restricts its application to HgCdTe. A more rigorous treatment must use a nonparabolic expression. Pratt et al. (1983) found that for Hg0:68 Cd0:32 Te ˛.E/ can be expressed as: a.E/ D 2  105 .E  Eg /3=2 cm1 :

(3.113)

Substituting (3.113) into (3.95), and considering that exp.Eg =kT /  1, B simplifies to: BD

1 n2i

30

1:29  10

.kB T /

9=2

!     Eg 2 Eg Eg C 8:75 s1 cm3 : exp  C5 kB T kB T kB T (3.114)

In addition, a simplified expression for B can also be obtained using the exponential fit to the absorption coefficient ˛.E/ D ˛g expŒˇ 0 .E  Eg /1=2 (refer to (4.136) of “Physics and Properties of Narrow Gap Semiconductors” (Chu and Sher 2007)).

3.4.3 Radiative Recombination in p-Type HgCdTe Materials From (3.105), we see that B D GR =n2i is a slow function of temperature, and therefore the concentration of majority carriers in n-type semiconductors can be taken to be a constant over quite a large range of temperatures in a nonintrinsic state. Consequently, the radiative recombination lifetime at moderate temperatures is also a slow function of temperature for n-type materials. However, this is not the case for p-type materials at lower temperatures, where the lifetime increases exponentially with temperature due to the carrier freeze-out effect in the low-temperature range. The relation between carrier concentration and temperature in this case can be obtained from the neutrality condition given by (3.115): n0 C Na D p0 C NdC ;

(3.115)

3.4 Radiative Recombination

157

where NdC and Na are concentrations of donor and acceptor ions, and n0 and p0 are the electron and hole concentrations at thermal equilibrium. Another factor is the compensation. At low temperatures, we have for a compensated semiconductor: p0 Š

Na  Nd Nv exp .Ea =kB T / : Nd g

(3.116)

While for an uncompensated semiconductor, i.e., p0  Nd , one finds:  p0 Š

Nv N a g

1=2 exp .Ea =kB T /

(3.117)

where Nv is the effective density of states at the top of valence band, and g is the degeneracy of the acceptors. Schacham and Finkman (1985) calculated the radiative lifetime of a p-type Hg0:785 Cd0:215 Te sample with Ea D 15 meV and Na  Nd D 1015 ; 1016 ; 1017 cm3 (Fig. 3.20). By comparing curves (2) and (3), we see that the recombination rate is decreased and the carrier lifetime is increased as a result of the decrease of the hole concentration induced by carrier freeze-out. From curves (1) and (2), the lifetime of a compensated semiconductor relative to that of an uncompensated one is increased since the lifetime R is proportional to Nd =.Na  Nd / in the case of compensation. Besides the freeze-out effect, background radiation also has an impact on the lifetime at low temperatures for Hg1x Cdx Te with small x. If the background temperature is a constant, the lifetime is a function of view angle, composition, and temperature of the device. The change of composition and temperature produces a change of the band-gap, therefore the cut-off wavelength. This results in a change of integrated background radiation. Figure 3.21 shows the temperature dependence of the background radiation flux at a view angle of 180ı and a background temperature

Fig. 3.20 Radiative lifetime of a p-type Hg0:785 Cd0:215 Te sample with Ea D 15 meV and various doping concentrations: (1) Nd D 0, uncompensated semiconductor, (2) Nd D 0:5Na , compensated semiconductor, and (3) without considering the freeze-out effect

158

3 Recombination

Fig. 3.21 Variation of background radiation flux as a function of temperature of HgCdTe

of 300 K for HgCdTe samples with different compositions (Schacham and Finkman 1985). We can see that for a Hg1x Cdx Te device with x D 0:22 the photon flux of a 300 K background radiation reaches a value of 1018 cm2 s1 when the device is held at low temperature. At low temperature p0 decreases exponentially, and thus the generation of excess carriers and radiative recombination processes are dominated by this background radiation. Due to the generation of excess carriers from the background radiation, the recombination rate increases which results in a negative impact on increasing the lifetime. So, the recombination lifetime does not increase exponentially at low temperatures and it faces a repression, see Fig. 3.22. This phenomenon is clearer for small x, even at higher temperatures. Figure 3.22 is a calculated result by Schacham. Figure 3.22a is the lifetime of HgCdTe samples with x D 0:25 and x D 0:29 at different doping concentrations, in which the background radiation effect has been considered. Figure 3.22b is the radiative lifetime of a HgCdTe sample with x D 0:215 at different doping concentrations and different view angles.

3.5 Lifetime Measurements of Minority Carriers 3.5.1 The Optical Modulation of Infrared Absorption Method Hg1x Cdx Te is a very important kind of semiconductor material in the fabrication of infrared detectors (Long and Schmit 1970; Tang 1974). Lifetimes of nonequilibrium carriers in Hg1x Cdx Te are deterministic performance parameters (Petersen 1970; Kinch et al. 1973; Bartoli et al. 1974; Gerhardts et al. 1978; Baker et al. 1978). Most research has focused on n-type Hg1x Cdx Te with a composition near

3.5 Lifetime Measurements of Minority Carriers

159

Fig. 3.22 (a) Radiative lifetime of Hg1x Cdx Te samples with x D 0:25 and x D 0:29 at different doping concentrations. The effects of background radiation have been taken into account. (b) Radiative lifetime of Hg1x Cdx Te with x D 0:215 at different doping concentrations and different view angles

x D 0:2.Eg  0:1 eV, 77 K). The methods for measuring lifetimes of nonequilibrium carriers include the classical photoconductivity decay rate, and the steady-state photoconductivity. These methods employ the decay of the photoconductivity to determine the minority carrier lifetime. In addition, techniques such as pulse recovery and electron beam induced current (Polla et al. 1981a) are also adopted in the research on p-type Hg1x Cdx Te. The carrier lifetime and the uniformity of its distribution are important in the fabrication of IR detectors, for example, in the manufacturing of SPRITE detectors (Elliott 1977 1981), where material having long carrier lifetimes exhibit the best performance. Therefore, in the selection of the best detectors, it is of great importance to use nondestructive techniques to measure the carrier lifetime. Optical Modulation of Infrared Absorption (OMIA) is a noncontact, nondestructive measurement technique. By using this technique, Afromowitz and Didomenico (1971) first experimentally determined the carrier lifetime of GaP.

160

3 Recombination

Then, Mroczkowski et al. (Mroczkowski et al. 1981; Polla et al. 1981b) reported the lifetime of carriers in near intrinsic and p-type Hg0:7 Cd0:3 Te at low temperature. The principle behind the operation of the OMIA technique for measuring the carrier lifetime of a semiconductor is that the optically generated carriers will affect the infrared absorption of free carriers, and thus the lifetime of excess carriers can be quantitatively determined. There are two independent light beams used in an OMIA experiment: a modulated pump beam with photon energy h Pump > Eg and a probe beam with photon energy h Probe < Eg . In the experiment, the probe-beam intensity passing through the sample without the modulated pump beam, I , is first measured, then the probebeam intensity passing through the sample with the pump beam present, I C I , where I is the peak amplitude of the modulated signal, is determined. The lifetime of photogenerated carriers can be obtained from the ratio I =I . Additional electron–hole pairs are generated in the semiconductor sample when the pump beam is applied, and as a consequence the probe-beam absorption of the sample increases from ˛.E/ to ˛.E/ C ˛.E/, and if n D p, then: 

˛.E/ D v2v1 .E/ C n .E/ C p .E/ p D  .E/p:

(3.118)

Here, v2v1 .E/ is the absorption cross-section of inter-band transitions from the light-hole band to the heavy-hole band, and n .E/ and p .E/ are absorption crosssections of intra-band transitions of electrons and holes, respectively. When the pump beam is applied, the transmission intensity of the probe beam passing through a sample of thickness d is:  Z I C I D I 1   .E/

d

 p.x/dx ;

0

Z

d

(3.119)

p.x/dx:

.I /=I D  .E/ 0

If surface recombination can be ignored, and the pump beam is totally absorbed within a depth much smaller than the diffusion length, then the stationary distribution of excess carriers is:

 p.x/ D .1  R /r Qp =L exp.x=L/;

(3.120)

where R is the reflectivity of pump radiation at the sample surface, r the quantum yield (the number of electrons excited per photon) for pump radiation of wavelength , Qp is the photon flux density, the lifetime, and L is the diffusion length. For pump photon energies greater than the band-gap, the quantum yield can be greater than one. From (3.118) and (3.119), we get: I =I D .1  R /r  .E/Qp Œ1  exp.d=L/ :

(3.121)

3.5 Lifetime Measurements of Minority Carriers

161

In a situation where the sample thickness d is much larger than the diffusion length L, then: (3.122) .I /=I D .1  R /r  .E/Qp : Equation (3.122) indicates that if R , r and  .E/ are known, then for a given Qp , the carrier lifetime can be obtained by measuring I =I . R is obtained from the refractive indices of HgCdTe (Baars and Sorger 1972); for pump radiation at  D 0:6328 m, then r D 3; and v2v1 is given in the literature (Mroczkowski et al. 1981): e2p2k v2v1 .E/ D nE„c



  Eg 4p 2  3ˇ



f exp.Ev1 =kB T / ; Nv

(3.123)

1 2 2 where  D .Eg2 C 8P 2 k 2 =3/1=2 ; ˇ D „2 .m1 0 C mhh /; Ev1 D „ k =2mhh ; P is the Kane momentum matrix element, n the refractive index, Nv the effective density of states in the heavy-hole band, f the fraction of holes in the heavy-hole band and is 0:75; mhh the effective mass of the heavy-hole band, and „k is the lattice momentum of the energy difference E (the photo energy of the probe) between the heavy-hole band and the light-hole band:

2

k D



4P 2 Eg  3ˇ 2 ˇ



2E   ˇ

"

4P 2 Eg  3ˇ 2 ˇ

2

16P 2 E  3ˇ 2

#1=2 :

(3.124)

Classical free carrier absorption formulas are adopted for calculating n and p (Moss et al. 1973): 2 e„ n C p D 137c 2 n



1 1 C 2 m2e e m h h

 ;

(3.125)

here e and h are electron and hole mobilities, respectively. The calculated results for probe beams with wavelengths  D 10:6 and 14:5 m, are given in Table 3.1. The configuration of an OMIA experiment is shown in Fig. 3.23. In the experiment, the probe beam is a CO2 laser . D 10:6 m/ and the pump beam is a He–Ne laser .0:6328 m/. The pathways of the probe beam and the pump beam are carefully adjusted so that the two beams aim at the same point on sample. The sample is placed in a container with windows, in which it is cooled by liquid nitrogen and the temperature can be controlled. A chopper is used to modulate the pump beam (or the probe beam). The transmitted intensity of the probe beam passing through the Table 3.1 Absorption cross-section Wavelength of the probe beam .m/ 2 1 .cm2 / 10.6 0:234  1015 14.5 0:218  1015

n .cm2 / 5:05  1013 =e 9:45  1013 =e

p .cm2 / 2:02  1012 =h 3:78  1012 =h

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3 Recombination

Fig. 3.23 The experimental setup for an OMIA measurement of the carrier lifetime Table 3.2 The material parameters and measured lifetimes of four HgCdTe samples 77 K 77 K 77 K 90 K 90 K Sample Composition  Eg ND  NA e x No. .x/ % (eV) .cm3 / .cm2 =v:s/ (s) Range of .s/ x 15 1 0.245 1.9 0.164 5:7  10 2:6  104 9:4  107 2:5  107 –1:8  106 2 0.325 1.3 0.292 1:1  1015 6:9  103 6:3  108 1:9  108 –1:6  107 3 0.34 2.4 0.315 4:7  1014 2:3  104 1:4  107 8:6  108 –2:6  107 4 0.265 3.5 0.195 5:7  1015 3:7  104 1:6  107 5:7  108 –2:8  107

sample without a pump beam present is, I , and is measured first; then the modulated pump beam is applied and the transmission intensity of the resulting output of the now modulated probe beam passing through sample, I C rI , is measured again. The modulation frequency is 800 Hz. The transmitted intensity is recorded by a Hg0:8 Cd0:2 Te photoelectric detector (cut-off wavelength: 12 m) operated at 77 K. The output signal of the detector is fed into a lock-in amplifier. In an OMIA experiment, a probe light with a continuous spectra (with long enough wavelengths) can also be used, but then the computations become complex. Ling and Lu (1984) using OMIA measured the carrier lifetime of n-type Hg1x Cdx Te with alloy concentrations between 0:24 < x < 0:35. The samples were prepared by solid-state re-crystallization, and processed by mechanical polishing, followed by chemical etching in a mixed solution of bromine–methanol, to a final thickness of 0.3–0.5 mm. The concentrations are determined by density and electron-probe measurements. The uniformity of the alloy concentrations and electric parameters are listed in Table 3.2. The power of probe beam Iprobe is limited to the order of a milliwatt, while the power of pump beam Ipump is 15 mW. Qp is calculated from the measured beam power by assuming a Gaussian beam distribution. The relation between I and I under the condition of a fixed pump beam power Qp D 5:4  1018 =s  cm2 is shown in Fig. 3.24, while the relation between I and I under the condition of fixed probe beam power Iprobe is shown in Fig. 3.25. The linear relations in Figs. 3.24 and 3.25 are consistent with (3.122) which means that for the above experimental conditions, the lifetime of carriers is independent of both the intensity of probe beam and the intensity of pump beam.

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Fig. 3.24 The linear curve of I vs. I for sample 3.x D 0:34/ under the condition of a fixed pump beam power Ipumb and temperature T D 300 K.Qp D 5:4  1018 =s cm2 ; .E/ D 1:5  10 15 cm2 , with slope I =I D 8:8  103 , the probe beam is a CO2 laser ( D 10:6 m) and the pump beam is a He–Ne laser (0:6328 m))

Fig. 3.25 The linear curve of I vs. Ipumb for sample No. 3 .x D 0:34/ under the condition of fixed-probe beam power Iprobe and temperature T D 300 K .probe D 10:6 m; pump D 0:6328 m/ and in this case the result is the same as that obtained in Fig. 3.24 . D 3:6  107 s/

In the condition Qp D 3:4  1018 =s  cm2 , the ratio of I =I i s measured for samples labeled 1–4 within temperatures ranging from 90 to 330 K. One needs to know the temperature dependence of  .E/ to obtain .T / from I =I . According to (3.123) and (3.125), the relation between the absorption crosssection  .E/ and the temperature is calculated in terms of the sample composition (determining Eg ) and the CO2 laser beam wavelength ( D 10:6 m or E D 0:117 eV). In the calculation, P D 8:5108 eVcm (Mroczkowski et al. 1981) and mhh D 0:55  m0 . Both me and Eg are cited from literature (Schmit 1970; Chu et al. 1982), and they are both alloy concentration and temperature dependent. For an ntype material, p can be neglected, because m2h h >> m2e e . The electron mobility e is obtained from the Hall effect and resistivity measurements. The calculated cross-section of sample No. 4 .x D 0:265/ probed by radiation with a photon energy E D 0:117 eV. D 10:6 m/ is shown in Fig. 3.26. It is apparent that at low temperature the cross-section is mainly determined by v1 v2 , while within the intrinsic temperature range the cross-section is mainly determined by n .

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Fig. 3.26 The cross-section of sample No. 4 .x D 0:265/ probed by a beam with E D 0:117 eV. D 10:6 m/

Fig. 3.27 The relation between lifetime and temperature of sample No. 4 .x D 0:265/, in which lifetime is dominated by Auger recombination. The data designated by “a” and “b” were taken by different groups

The relation between lifetime and temperature T can be obtained from (3.122) with experimental I =I data and calculated values of  .E/. These relations for samples No. 4 .x D 0:265/ and No. 2 .x D 0:325/ are shown in Figs. 3.27 and 3.28, respectively. These two groups of experimental data correspond to two different test positions “a” and “b” on the samples.

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Fig. 3.28 The relation between lifetime and temperature of sample No. 2 .x D 0:325/, in which the lifetime is dominated by Shockley–Read recombination. The data designated by “a” and “b” were taken by different groups

Fig. 3.29 The distribution of lifetimes over a plane with the probe spot moved in 1 mm steps (Sample No. 3, x D 0:34; T D 90 K)

The distribution of carrier lifetimes over a plane has also been measured by scanning the probe spot with a step length of 1 mm at 300 and 90 K. The resulting distributions for sample No. 3 .x D 0:34/ at 90 K is shown in Fig. 3.29. Let’s analyze the experimental results for various carrier recombination mechanisms. If there are no recombination centers, then the carrier recombination mechanisms include only radiative recombination and Auger recombination.

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3 Recombination

Under a weak excitation condition, the lifetime for radiative recombination is:

R D

1 : B.n0 C p0 /

(3.126)

For an intrinsic semiconductor, n0 D p0 D ni , the radiative lifetime dependence reduces to: 1 : (3.127)

Ri D 2Bni Here, B is the capture probability for minority carriers. By assuming (a) the energy band structure is parabolic near k D 0, (b) the carriers obey Boltzmann statistics, and (c) the theoretical formula for the absorption coefficient is adopted, B can be written as (Hall 1959):   3=2   m0 m0 300 3=2 m0 1 C C : B D 5:8  1013 "1=2 1 me C mh me mh T    Eg2 C 3kB TEg C 3:75kB2 T 2 Under a weak excitation condition, for a semiconductor material with  D the Auger recombination lifetime is (Blakemore 1962): 1=2 .1 C 2/

Ai D 3:8  1018 "1=2 1 .1 C / " #1     3=2 me 1 C 2 Eg 2 kB T ;  exp jF1 F2 j m0 Eg 1 C  kB T

(3.128) me  1, mh

(3.129)

in which F1 F2 is the product of Bloch function overlap integrals between the conduction and valance bands, and the conduction band edge and an excited level in the conduction band (Auger 1). For an n-type material, the Auger lifetime reduced to the expression:

A D

2 Ai n2i : n0 .n0 C p0 /

(3.130)

Both the radiation recombination lifetime R and the inter-band collision recombination lifetime A depend on the composition .x/ of Hg1x Cdx Te, the temperature .T / and the net donor concentration .ND  NA /. According to the report of Baker et al. (1978), if x is small then A 6 R , i.e., the lifetime is dominated by collision induced recombination, but with an increase of x, A increases rapidly while R decreases slowly, which means there is a critical composition .xc /, for which if x > xc then A  R , and the lifetime is dominated by radiative recombination. The critical composition is related to temperature and the net donor concentration, for the case of ND  NA D 1  1015 cm3 and T D 90 K, then xc  0:3.

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If there is a recombination center with energy level ET and density NT , existing within the energy gap, electrons and holes can recombine via this center. For a condition in which NT  n0 and weak excitation, the lifetime in the “steadystate approximation” can be expressed by the Shockley–Read formula (Shockley and Read 1952): n 0 C n1 p 0 C p1

D p0 C n0 ; (3.131) n0 C p0 n0 C p0 where n1 and p1 are the concentrations of electrons and holes if the Fermi level coincides with the energy of the recombination center, while p0 D .NT cp /1 ,

n0 D .NT cn /1 , here cn and cp are, respectively, the recombination center’s capture coefficients for electrons and holes. For an n-type sample, within a nonintrinsic temperature range, because n0  p0 , n0  n1 , p1  p0 , then (3.131) can be simplified:

SR D p0 C n0

p1 Nv exp Œ.Ev  ET /=kB T  D p0 C n0 : n0 n0

(3.132)

Within this range of temperatures, n0 D ND  NA , and it is a temperature independent constant. If the lifetime is dominated by the recombination center mechanism, i.e., is smaller than R or A , then the lifetime varies exponentially with temperature following the relation in (3.132). We can analyze the experimental results by using above recombination theory. The relation between the lifetime vs. temperature of sample No. 4 .x D 0:265/ is shown in Fig. 3.25. The solid and dashed curves are theoretical lifetimes due to collision induced recombination and radiative recombination computed from (3.127) to (3.130). The results show that, for the same net donor concentration,

R is greater than A by an order of magnitude. The two groups experimental data given in the figure can be fitted by theoretical values with n0 D 2:8  1015 and n0 D 4:8  1015 cm3 , respectively. The net donor concentrations n0 used to fit the experimental data are in accord with the results of Hall-effect measurements. (See Table 3.2.) For the intrinsic temperature T D 250 K, the experimental data lies close to the theoretical lifetime Ai due to intrinsic collision recombination. Therefore, no matter whether the temperature is at the edge or above the intrinsic range, the lifetime of sample No. 4 is dominated by inter-band collision recombination. The difference between the two groups experimental data reflect that the experiments were conducted on different locations on the samples, which means the net donor concentration was nonuniform. Similar results were obtained on sample No. 1 .x D 0:245/. The lifetime vs. temperature of sample No. 2 .x D 0:325/ is shown in Fig. 3.13. We find that at low temperature the experimental lifetime is lower than that of the theoretical radiative recombination prediction (90 K, n0 D 1:1  1015 cm3 ,

R D 8:2  106 s) by two orders of magnitude. Within the nonintrinsic temperature range, the relation between the lifetime and temperature follows the characteristics of Shockley–Read recombination, and can be described by (3.130). For “group a”

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experimental data, given p0 D 66 ns, the energy level of the recombination center ER can be obtained from the slope of the expression: ln.  p0 /=T 3=2 

1 : T

(3.133)

Extracted from (3.133), from which we get ET  EV C 30 meV. Within the intrinsic temperature range, where the lifetime is dominated by recombination via a recombination center, the lifetime severally deviates from that of an intrinsic collision recombination process. The differences between the two groups’ data in the figure reflect the fact that the density of recombination centers NR differs at different positions. Similar results are obtained for sample No. 3 .x D 0:34/, in which E D jET  Ev j  40 meV. The distribution of a typical lifetime obtained by sweeping the probe beam spot over a plane is shown in Fig. 3.27, it is the data measured on sample No. 3 .x D 0:34/ at T D 90 K. It is obvious that the lifetimes differ from position to position, and decrease at grain boundaries. The planar distribution of the lifetimes at T D 300 K is nearly the same as that at T D 90 K. This can also be seen from the relation between lifetimes and temperature for different sample positions shown in Figs. 3.25 and 3.26. The range of lifetimes for all samples at T D 90 K are listed in Table 3.2. According to these lifetime vs. temperature measurement results, for different samples and probe spot positions, we conclude that the variation of lifetimes originates from fluctuations of the net donor concentration or a nonuniform distribution of recombination centers. According to (3.126) and (3.130), for radiative recombination R is proportional to 1=n0 , and for inter-band collision recombination A is proportional to 1=n20 . For recombination via a recombination center (Shockley– Read recombination), at low temperature, S–R = po D .NR cp /1 , i.e., the lifetime

S–R is proportional to 1=NT . There are various defects in a HgCdTe semiconductor, in which a donor (a Hg interstitial atom), an acceptor (a mercury vacancy), and the density of defect energy levels are related to thermal processing conditions (Tang 1976), so it is easy to understand why there are fluctuations of the net donor concentration, or a nonuniform distribution of recombination centers. In the measurement of carrier lifetimes of n-type Hg1x Cdx Te materials, compared to classical stationary state photoconductivity or photoconductivity decay, the OMIA technique has the following virtues: it offers a noncontact, nondestructive, point by point measurement technique through probe scanning. If appropriate probe beams .h Probe < Eg / and pump beams .h Pump > Eg / are selected, the OMIA technique can also be used for other semiconductor materials. For example, the carrier lifetime in an n-type InSb sample with a net donor concentration n D 4:5  108 s measured by an OMIA technique at room temperature, resulted in D 4:5  108 s (the absorption cross-section used in the calculation is cited in the literature (Kurnick and Powell 1959)). This value coincides with the lifetime of InSb determined to be due to intrinsic collision recombination at 300 K reported by Huang and Tang (1965).

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3.5.2 The Investigation of Minority Carriers Lifetimes in Semiconductors by Microwave Reflection Although photoconductivity decay is a simple technique for measuring the lifetime of minority carries, it has the disadvantage of requiring that two contact electrodes be added at both sides of wafer which can induce damage in the material. Microwave reflection is a noncontact technique for measuring the minority carrier lifetime. Using this technique, the contact electrodes are eliminated and any damage to the sample can be avoided. When a light beam pulse with photon energy greater than energy gap irradiates a semiconductor, nonequilibrium carriers are generated. A sketch of the measurement system of the nonequilibrium carrier lifetime by direct current photoconductivity is shown in Fig. 3.30. The decay of the photoconductivity with time can be observed directly on the screen of oscilloscope (an exponential decay), thus the lifetime can be obtained from the photoconductivity vs. time curve. A sketch of the system for measuring the minority carrier lifetime by microwave reflection is presented in Fig. 3.31. If a light-beam pulse and a high-frequency electromagnetic wave (microwave) simultaneously irradiate a semiconductor sample, the variation of microwave reflectivity induced by the change of the conductivity generated by a light beam pulse is: R D R. C  /  R. /;

(3.134)

Fig. 3.30 A sketch of the system for the minority carrier photoconductivity decay lifetime measurement

Fig. 3.31 The configuration of a microwave reflection technique for measuring the minority carrier lifetime

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3 Recombination

where  is conductivity and  is photo-induced change in the conductivity. For a small light injection condition, (3.134) can be written as: R D

@R. /  : @

(3.135)

Within the microwave band, the reflectance is highly sensitive to the conductivity, therefore the variation of the reflectance can accurately measure its decay and the nonequilibrium carrier lifetime. The configuration of a microwave reflection apparatus for measuring the minority carrier lifetime suggested by Mao and Chu (1993) is shown in Fig. 3.31. A pulsed light beam (wavelength 0:83 m, power 10 mW) emitted from a semiconductor laser irradiates a sample; while microwave radiation (wavelength 8 mm, power 10 mW) generated by a Gunn’s oscillator, after passing through isolator, attenuator and circulator, and transmitted out via a horn antenna also irradiates the sample. The microwave power irradiates the same position as the pulsed light beam. The reflected microwave power is received by the horn antenna, and via a circulator and a detector, is fed into an oscilloscope (TDS520). Information about the photoconductivity decay and the nonequilibrium carrier lifetime is obtained from the transient variation of the reflected power with time. In order to compare the lifetimes measured by both photoconductivity decay (PCD) and microwave radiation (MR) under equivalent experimental conditions, contact electrodes are placed on both sides of samples. Then, both the PCD and MR methods can be applied at the same position. These two methods were used to measure the lifetimes at different positions on two samples, the experimental results are shown in Figs. 3.32, 3.33, and 3.34. The parameters of the HgCdTe samples are listed below: No. 1: x D 0:4, n D 2:3  1015 cm3 , 300 K; n D 1:38  1014 cm3 , 77 K. No. 2: x D 0:4, n D 1:78  1015 cm3 , 300 K; n D 6:4  1013 cm3 , 77 K.

Fig. 3.32 The minority carrier lifetime in HgCdTe obtained by MR and PCD

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171

Fig. 3.33 The minority carrier lifetime for different positions on a HgCdTe sample measured by MR

Fig. 3.34 A comparison of the minority carrier lifetimes measured by MR and PCD

It can be seen from the experimental results (see Fig. 3.32) that the minority carrier lifetime measured by MR basically coincides with that of PCD. The minority carrier lifetime for different positions on a sample was also measured by MR, and the results are shown in Fig. 3.33, where it is obvious that the lifetime varies with position. While there is a little difference between the lifetimes obtained by MR and PCD, the lifetimes obtained by MR are generally longer than those obtained by PCD. There are differences of the lifetimes measured at different positions on the same sample using MR and PCD, as shown in Fig. 3.34. In a PCD measurement, two electrodes are necessary one on each side of the sample, and a bias voltage must be applied to the electrodes. Because the measured conductance responds not only to the region irradiated by the light beam pulse but also to adjacent regions, this can cause a relatively large error in the measured conductance. While in the MR measurement, the reflected microwave power transient is mainly determined by the photoconductive decay of the irradiated region. Therefore, the lifetimes measured by MR are more accurate than those of PCD.

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3 Recombination

3.5.3 The Application of Scanning Photoluminescence for Lifetime Uniformity Measurements In the fabrication of Hg1x Cdx Te focal plane devices, rigorous material measurement techniques are required. Not only the net nature of material but also the property distribution of tiny regions must be tested. Therefore, many relevant test means have been proposed (Gong 1993; Bajaj et al. 1987; Kopanski et al. 1992; Mao and Chu 1993). These test means, however, often require the preparation of electrodes on samples, which restricts wide applications of such techniques. Because of its nondestructive and noncontact character, the spot scanning PL technique over a plane has been widely used to test semiconductor materials (Hovel 1992). But for Hg1x Cdx Te, radiative recombination of the photo-generated nonequilibrium carriers causes only a small portion recombination process, while other factors (including thermal background radiation) have a comparatively large effect, which introduces some difficulties into the study. Here, we introduce a Fourier transformation infrared PL technique coupled to a scanning PL measurement. Adopting this technique enables both the surface composition and the nonequilibrium carrier lifetime distributions to be obtained. Samples selected for scanning PL experiments have included Sb-doped and undoped Hg1x Cdx Te single crystal wafers. The selected samples are first etched in a methyl–alcohol solution in order to reduce negative effects due to surface recombination. Then, the sample is placed in a dewar with windows, in which the sample is liquid nitrogen cooled to a temperature of 77 K. The dewar is fixed on a scanning mechanical framework, which moves it in a plane parallel to the sample’s surface. The precision of this movement is controllable within 10 m. A continuous-wave (cw) ArC 514:5 nm laser is used to excite the front surface of sample. The resulting luminescence is then collected by a parabola mirror and fed into Nicolet 800 Fourier transform spectrometer, after which the signal is finally received by an InSb or a HgCdTe detector operated at 77 K, that is included in Nicolet 800 spectrometer. The Laser can be focused according to different needs of devices, and the mechanical scan system can be set to different step lengths to get different spatial resolutions. The best spatial resolution of this system is 20 m. It should be pointed out that the scanning is carried out by moving the sample, while the path of laser beam is unchanged during the whole experimental process. In this way, a comparison of the PL intensity from different areas of a sample’s surface can be generated. First, we examine the compositional uniformity of Hg1x Cdx Te samples. The PL spectra for different positions on a sample’s surface are shown in Fig. 3.35. The sample is a part of an Sb-doped Hg1x Cdx Te wafer. Above 50 K, the high-energy side of the PL peak has the highest intensity, the relation between the peak’s location and temperature is the same as that between the energy gap and temperature, which means this peak corresponds to a transition from the conduction band to the valence band. A two-dimensional distribution is shown in Fig. 3.36 of peaks’

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Fig. 3.35 The photoluminescence spectra of Sb-doped HgCdTe samples at 77 K

Fig. 3.36 A planar distribution of photoluminescence peak locations

locations after irradiation excited transitions among the bands. Ignoring a 1–2 meV deviation caused by self-absorption in the sample, the peak energies are equal to the band-gap .Eg /. Thus, from the empirical equation (Chu et al. 1983, 1994) that provides a relation among Eg and composition (x) and temperature (T ), the composition of a sample and its distribution over a plane can be deduced. Moreover, the Urbach band tail has no effect on the planar location distribution of a PL peak, therefore, a more accurate compositional (x) distribution results as Fig. 3.37 indicates. From Fig. 3.37, we learn that the composition distribution is not homogeneous. There is a larger value on the rim of the wafer, while there is a smaller value near the center. The reasons for these observations are concluded to be: First, during the crystal growth process, if the solid–liquid interface is concave to the melt, the Cadmium composition x will condense first in the peripheral region and will occupy relatively more sites; Second, because the density of a HgTe solution is higher than that of HgCdTe, gravity in a vertical crucible will cause a surplus of HgTe to separate out during crystallization of melt, so it will aggregate in the middle of a concave interface. If we want a larger

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3 Recombination

Fig. 3.37 A planar distribution of the composition

x value in a grown crystal, there will be a larger proportion of CdTe in the melt; consequently, the horizontal homogeneity will become worse (Jones et al. 1982). Therefore, it is quite important to maintain a planar solid–liquid interface during the HgCdTe crystal growth process to ensure horizontal homogeneity of the crystal. We can analyze the lifetime uniformity of HgCdTe samples through scanning PL spectra. In bulk Hg1x Cdx Te, there are three kinds of recombination mechanisms for photo-generated nonequilibrium carriers, radiative r , Shockley–Read SR , and Auger A recombination. PL is directly produced by radiative recombination. At low temperature, the concentration of light-generated minority carriers is much larger than that of equilibrium carriers, for p-type Hg1x Cdx Te material (n  n, n and n are the concentrations of electrons and photo-generated nonequilibrium carriers, respectively). The recombination rate equation including all mechanisms mentioned above can be written as:

in which

˛I0 n dn D  ; dt „!ex

(3.136)

1 1 1 1 D C C ;

r

SR

A

(3.137)

where ˛ is the absorption coefficient of radiation with energy „!ex , I the power density of this radiation,  the quantum efficiency, and is the net lifetime of the photo-generated nonequilibrium carriers. The intensity of PL IPL / n= r . Keeping the intensity of the laser constant, the concentration of carriers will not vary with D 0, then: time, thus dn dt ˛I0 : (3.138) nD „!ex The intensity of PL is: IPL / n= r D

˛I0 ˛I0 D „!ex r „!ex

 

:

r

(3.139)

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175

Fig. 3.38 This sample’s measured two-dimensional photoluminescence intensity distribution shows a rather great discreteness

Equation (3.139) indicates that the fraction of radiation recombination to the overall recombination lifetime of nonequilibrium carriers can be calculated from the measured PL intensity. According to the calculated results of Schacham and Finkman (1985), the lifetime of inter-band direct radiation recombination is:

r D

1 ; B.n C p/

(3.140)

where B is the same as that in (3.99). Some samples exhibit areas where strong intensity variations overwhelm the tiny differences caused by the compositional heterogeneity. For a sample of this sort, the two-dimensional PL intensity distribution is shown in Fig. 3.38 (the sample is the same as the one mentioned in Fig. 3.35). Here, there is a rather great discreteness in PL intensity, which can be explained by a highly dispersed distribution of nonequilibrium carrier lifetimes. Possible mechanisms within bulk Hg1x Cdx Te include crystal defects such as dislocations, sublattice interfaces, lattice deformations, and glide planes. As mentioned previously, these defects could cause deep energy levels in the band-gap and decrease local nonradiation recombination lifetimes. We see from Fig. 3.39 that the PL intensity in the middle of this wafer is higher than that at the edge. This means that the lattice exhibits better integrity in the middle of the wafer and correspondingly the lifetime of light-generated nonequilibrium carriers is longer. The extra nonradiative lifetime reduction is likely due to a surfaceassisted recombination mechanism. The negative effect of lattice imperfections can be identified directly from the following experimental results. A nick is intentionally made on the sample examined in Fig. 3.39, and the PL intensity distribution near the nick is shown in Fig. 3.40. We can see in Fig. 3.40 an obvious PL intensity decrease of about 1–2 orders of magnitude relative to that shown in Fig. 3.39 at the nick. This indicates that the ratio of radiative recombination to the total recombination decreases greatly at the nick. If the resolution of the mechanical system is further improved, lattice defects such as dislocations, and slip planes can be distinguish. In fact, by using this method, the defects mentioned earlier have been observed in GaAs (Hovel 1992).

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Fig. 3.39 Peak intensity distribution of band to band photoluminescence (the same sample as used in Fig. 3.38)

Fig. 3.40 The change of photoluminescence intensity after a nick is made on the surface of the same as used in Fig. 3.39

3.5.4 Experimental Investigation of Minority Carrier Lifetimes in Undoped and p-Type HgCdTe There has been much experimental research reported on the minority carrier lifetimes of HgCdTe. Chen measured the minority carrier lifetimes of p-type HgCdTe with hole concentrations ranging from 1  1015 to 5  1015 cm3 , as well as undoped LPE films (Chen et al. 1987). Tung measured minority carrier lifetimes of As-doped LPE films with hole concentrations ranging from 51015 to 21017 cm3 (Tung et al. 1987). Lacklison and Capper (1987) measured sample lifetimes with hole concentrations ranging from 3  1015 to 2  1017 cm3 . By simulating a temperature-dependence of lifetimes, Lacklison identified an SR recombination center at Ev C 0:015 eV. Souza et al. (1990) measured the minority carrier lifetimes of un-doped MBE films with x ranging between x D 0:2 and 0.3, and found that they mainly depend on an SR recombination center near the middle of band-gap. Adomaitis et al. (1990) measured the minority carrier lifetimes of undoped LPE films, according to his result it is as short as 53 ps. Adomaitis believed

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177

that the minority carrier lifetime in the samples with hole concentrations higher than 4  1016 cm3 is dominated by the Auger 7 process. For further study on the relation between minority carrier lifetimes of HgCdTe films vs. temperature and hole concentration, as well as comparisons of the recombination mechanisms in doped and undoped HgCdTe samples, see the literature (Chen et al. 1995). The minority carrier lifetime of p-type HgCdTe depends on Auger 1, Auger 7, radiative and S–R recombination process: 1 1 1 1 1 C C C : D

A1

A7

R

SR

(3.141)

Under a situation where there is degeneracy:

A1 D

A7 D rD

Ai 7

Ai 1

2n2i Ai 1 .n0 C p0 /n0 2n2i Ai 7 .n0 C p0 /p0

m .ET / Š2 e  m0

;

(3.142)

;

(3.143)

1  5=4 T 1  3=2 T

! :

(3.144)

Here, m0 is the electron effective mass at the bottom of the conduction band, me .ET / is the effective mass of an electron with energy ET higher than the bottom of the conduction band, and T D ET =kB T D Eg =kB T . Equations (3.142) and (3.143) fit data for carrier concentrations up to 11018 cm3 at 77 K. In general, for p-type HgCdTe, an Auger 1 process is important only at higher temperatures (generally higher than 150 K). Especially within the lower part of this range of intrinsic temperatures, the Auger 7 process plays a key role. The factor jF1 F2 j for the Bloch wave-function overlap integrals, which is necessary for calculating the lifetime determined by an Auger recombination process, is obtained by fitting to experiments. Its value is about 0.15–0.2 (Chen and Colombo 1992). The value of r D Ai 7 = Ai 1 is 2 for Hg1x Cdx Te with x D 0:2 (Casselman 1981). It is also obtained by fitting experiment results to (3.134) where the result obtained is thought to be relative more exact. More precise calculations of jF1 F2 j based on proper band structures show that in fact this factor depends on k and temperature T , and these constant values are only rough approximations (Krishnamurthy et al. 2006). Chen et al. (1995) measured at 77 K the relation between the lifetime vs. the carrier concentration in LPE grown Hg1x Cdx Te .x D 0:225/ films. The experimental and fitted computational results are shown in Fig. 3.41. In this figure, the solid curve is a fitted lifetime considering only Auger 7 and radiative recombination processes. The circles, diamonds, and triangles denote experimental lifetime data for Au-doped, Cu-doped, and undoped samples, respectively. The undoped sample is p-type in which the acceptors are Hg vacancies. The dashed curve is fit to the variation of the lifetime of an undoped sample. It is obvious that when the concentration of carriers lies below

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Fig. 3.41 Relations between the lifetimes and the carrier concentrations at 77 K for LPE grown Hg1x Cdx Te.x D 0:225/ films. The solid curve is a calculated lifetime considering only Auger 7 and radiative recombination

Fig. 3.42 The relation at 77 K between the lifetimes and carrier concentrations for LPE grown Hg1x Cdx Te.x D 0:225/ films. The solid curve is a fitted lifetime only considering radiative recombination

1  1017 cm3 , the lifetime of doped samples (2–8 ns) is longer than that of an undoped sample (150–8 ns). A possible reason is due to S–R recombination centers associated with Hg vacancies which reduces the lifetime. In order to determine the contribution from radiative, Auger 7 and Auger 1 recombination to the lifetime of doped samples (x D 0:225, the same as that used in Fig. 3.41) at 77 K, the value of  D Ai 7 = Ai 1 is set to 10, 20, 30, and the corresponding calculated results are shown in Fig. 3.42 (dashed lines). We find that  D 20 provides the optimum fit to the experimental results (circles and diamonds denote experimental lifetime data of Au-doped and Cu-doped samples). In contrast, the calculated result considering only radiative recombination is also presented in the figure (the solid line). According to this result, we conclude that radiative recombination is the major recombination mechanism at 77 K if the concentration of carriers is lower than 5  1015 cm3 .

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179

Fig. 3.43 (a) The relation between lifetime and reciprocal temperature for a Cu-doped LPE HgCdTe. The carrier concentration is 2:6  1015 cm3 . (b) The results including Auger 7 and Auger 1 processes and  D Ai 7 = Ai 1 D 20

There is no S–R recombination contribution for the Au-doped and Cu-doped LPE samples presented in Fig. 3.41. This is also true in temperature-dependent lifetime measurements. The relation between the minority carrier lifetime and temperature for an Hg1x Cdx Te sample (x D 0:222) is shown in Fig. 3.43a. The dashed curve labeled AUG is the lifetime due to Auger 7 and Auger 1 processes, while the dashed curve labeled RAD is the lifetime due to radiative recombination. This sample is Cu-doped, and the carrier concentration is 2:6  1015 cm3 . In samples with lower carrier concentrations, radiative recombination dominates at lower temperatures (lower than 150 K), while Auger recombination dominates at higher temperatures. The solid curve is the net lifetime including Auger and radiative recombination. In the calculation, Auger recombination includes both Auger 7 and Auger 1 processes, and setting  D Ai 7 = Ai 1 D 20; if  D 30 or 10, there is a little difference at higher temperatures, as shown in Fig. 3.43b. In undoped p-type LPE samples, with the p-type conduction mainly due to Hg vacancies, both the Hg vacancies and the impurities play roles as recombination centers. Therefore, at low temperature, the main recombination process changes from a radiative recombination mechanism to a S–R recombination mechanism. The calculated relation between the lifetime and temperature is shown in Fig. 3.44, where the three dashed lines labeled SRH, RAD, and AUG represent their respective contributions to the recombination lifetime. The solid line is the optimum simulated lifetime obtained by considering all contributions from the above three recombination mechanisms. The data points are experimental values. The samples are p-type

180

3 Recombination

Fig. 3.44 The calculated curves for the lifetime vs. the reciprocal temperature. The three dashed curves labeled SRH, RAD and AUG are the contributions of SR, radiative and Auger recombination to the lifetime, respectively. The solid line is the optimum simulated lifetime obtained by considering all contributions from the above three recombination mechanisms

Hg1x Cdx Te films grown by LPE with x D 0:225, the carrier concentration is 4:81015 cm3 . The parameters for obtaining an optimum simulation are: the crosssection of S–R recombination center for electrons and holes are n D 11016 cm2 and p D 5  1019 cm2 , respectively, the recombination center concentration is Nr D 8  1014 cm3 , and the recombination center energy level is located in the middle of the energy gap. We next offer comprehensive experimental results for the minority carrier lifetimes of n-type HgCdTe. Wijewarnasuriya et al. (1995) measured the minority carrier lifetimes of in In-doped HgCdTe films. Samples were grown by MBE on CdZnTe (211B) substrates. The indium is doped in situ, and the as-grown films are then annealed under an Hg saturated atmosphere at 250ı C in order to decrease Hg vacancies. The minority carrier lifetime is measured using the photoconductivity decay method. In n-type samples, the major Auger recombination process is Auger 1: 2n2i Ai 1

;

(3.145)

2 Ri ni ; .n0 C p0 /

(3.146)

p0 .n0 C n1 /

n .p0 C p1 / C 0 ; n0 C p0 n0 C p0

(3.147)

A1 D

.n C p/n

the radiative recombination lifetime is:

R D and the S–R recombination lifetime is:

SR D

3.5 Lifetime Measurements of Minority Carriers

181

Fig. 3.45 The lifetime vs. the reciprocal temperature in Indium lightly doped HgCdTe. Circles and diamonds are experimental data, and curves are results calculated to fit the experimental data

where n0 and p0 are the shortest electron trap and hole trap time constants, n1 D n0 exp.ET  EF /=kB T , p1 D p0 exp.ET  EF /=kB T , and ET is the energy level of a S–R recombination center. The experimental and calculated results for the lifetimes vs. the reciprocal temperature are shown in Fig. 3.45. It is obvious that the lifetime increases up to a maximum with a decrease of the temperature, and then the lifetime decreases with a continuing decrease of the temperature. The parameters for the sample’s data in Fig. 3.45a are as follows: x D 0:217, thickness t D 8:7 m, ND D 1:41015 cm3 ,  D 1:6105 cm2 =Vs, and n0 D 1:31015 cm3 . At 80 K, 80 K D 940 ns is found. The two dashed curves in the figure are the calculated net lifetimes due to radiative and Auger recombination. We see that at 130 K the lifetime has a maximum (1:4 s). At lower temperatures, the lifetime decreases exponentially. The results for samples #8275 and #8281 are shown in Fig. 3.45b, in which the data points are experimental results and the solid curve is the calculated lifetime including both Auger and radiative recombination. The parameters for sample #8275 are as follows: x D 0:244, t D 9:5 m, ND D 2:11016 cm3 ,  D 1:0105 cm2 =Vs, n0 D 1:11016 cm3 , and D 20 ns (80 K). The maximum lifetime is max D 100 ns. The parameters for

182

3 Recombination

Fig. 3.46 The lifetime vs. the electron concentration at 80 K for an In-doped HgCdTe sample grown by MBE

sample #8281 are as follows: x D 0:237, t D 11:5 m, ND D 4:0  1015 cm3 ,  D 1:0  105 cm2 =Vs, n0 D 3:1  1015 cm3 , and D 184 ns (80 K). Generally, we calculated the net lifetime including Auger and radiative recombination and compare it to the measured 1=T experimental data. At low temperatures, if the calculated values are greater than that of the experiment, the interpretation is that there is a contribution from S–R recombination. In the calculation of the Auger recombination lifetime, the factor jF1 F2 j for the Bloch wave-function overlapped integrals is selected to fit the experimental lifetime results given the carrier concentration at low temperature (77 K). The lifetime vs. the electron concentration of an In-doped HgCdTe grown by MBE is shown in Fig. 3.46 (80 K). When the electron concentration increases from 1:4  1015 to 1:0  1016 cm3 , the lifetime decreases from 950 to 20 ns. Supposing there are no SR recombination centers in n-type samples, then the Auger recombination dominates at low temperature. According to (3.145), A / n2 0 , by changing the value of jF1 F2 j, the optimum simulation is obtained when jF1 F2 j D 0:22. For a HgCdTe device, there is an anodic oxide layer or passivation layer on its surface. This layer is degraded by being irradiated by an ultraviolet light when it is applied, because electrons in the passivation layer are then excited from the valence band to the conduction band and subsequently captured on otherwise neutral trapping centers, as showed in Fig. 3.47. This permanently changes them. Therefore, electrons in the accumulation layer of a HgCdTe surface will easily recombine with holes in valence band in the passivation layer, causing carrier lifetimes to decrease. The experimental results for the lifetime including the results before and after ultraviolet irradiation are showed in the following figure. Data points are experimental values, and real curves are fitted calculated results (Staszewski and Wollrab 1989).

3.6 Surface Recombination

183

Fig. 3.47 The relation between carrier lifetimes and reciprocal temperatures before and after ultraviolet irradiation

3.6 Surface Recombination 3.6.1 The Effect of Surface Recombination Due to crystal imperfections, the potential field periodicity is destroyed and additional energy levels are generated in the forbidden band. Tamm (1932) first pointed out in 1932 that: The existence of a crystal surface makes the periodic potential field cut off at the surface to cause additional energy levels. The situation at real surfaces is more complicated because of the existence of oxidization and impurities. Here, we only discuss a one-dimensional crystal surface under an ideal situation. Figure 3.48 shows the potential energy variation at an ideal one-dimensional crystal surface located at x D 0; x > 0 corresponds to inside the crystal where the potential energy changes periodically with x. A cycle length is a, so the potential energy function is V .x C a/ D V .x/. x < 0 corresponds to the area beyond the crystal where the potential energy is a constant V0 . For such a semi-infinite periodic potential field, the wave function of an electron obeys the Schr¨odinger equation: 

„2 @2 C V0 2m0 @x 2

DE

.x 0/

(3.148)

and 

„2 @2 C V .x/ 2m0 @x 2

DE

.x  0/:

(3.149)

184

3 Recombination

Fig. 3.48 The potential energy function for an ideal one-dimensional crystal

Consider the situation of an electron with energy E < V0 , and using the condition that the wave functions has a limited displacement at ˙1, then solving the abovementioned two equations, we find: x 0

1

! p 2m0 .V0  E/ x D A exp „

(3.150)

and x0

2

D A1 uk .x/ exp.i2kx/ C A2 uk .x/ exp.i2kx/:

(3.151)

Because of the continuity of wave functions and their first derivatives, we know that: A1 uk .0/ C A2 uk .0/ D A;

(3.152)

and p A1 Œu0k .0/

C i2kuk .0/ C

A2 Œu0k .0/

 i2kuk .0/:

DA

2m0 .V0  E/ „ (3.153)

The three coefficients A1 ; A2 , and A are determined by the above two equations. If k is a real number, the wave functions are limited at x ! ˙1, so both coefficients A1 and A2 can be nonzero. Equations (3.152) and (3.153) constitute two equations in three unknowns. The third equation is the normalization condition. These solutions are the permissible states in this potential field, while the corresponding levels are the allowed energies. When k is a complex number, k D k 0 C ik 00 , where both k 0 and k 00 are real numbers, then (3.151) becomes: 2

D A1 uk .x/ exp.i2k 0 x/ exp.2k 00 x/ CA2 uk .x/ exp.i2k 0 x/ exp.2k 00 x/:

(3.154)

3.6 Surface Recombination

185

We know that when x ! ˙1, 2 must be finite, this means in a one-dimensional infinite periodic potential field, k can’t be a complex. While in a one-dimensional semi-infinite periodic potential field, if A1 or A2 equals to zero, k can be complex. For example: if A2 D 0, then: 2

D A1 uk .x/ exp.i2k 0 x/ exp.2k 00 x/:

(3.155)

We find that if k > 0 then 2 is limited, so there are solutions. Solving (3.150) and (3.151), knowing that both A and A1 are nonzero yields: EDV 

„2 2m0



u0k .0/ C i2k uk .0/

2 :

(3.156)

In this instance, we find that on both sides of x D 0, the wave functions decay exponentially. This indicates that the electron distribution is concentrated around x D 0, indicating that the electron is bound near the surface. At the surface, k is complex and so is the surface energy. Tamm (1932) calculated a semi-infinite Kronig–Penney model, and proved that given a certain condition, each surface atom has a corresponding surface energy level, with a magnitude of about 1015 cm2 . For a “pure silicon surface” under an ultra-high vacuum the surface-state density was measured, and it indicated that the density of surface states coincides with this theory, and its magnitude is about proportional to the dangling-bond density of surface atoms. Therefore, this finding is explained because a crystal lattice terminates suddenly at a surface, producing the appearance of an unmated atom and a corresponding electron surface state. The surface of HgCdTe is generally processed by a passivation technology (commonly, an anodic oxidation or a CdTe layer), so there is often an oxidized layer on its surface (including natural oxidation in ambient air). Then, the dangling bonds are saturated by oxygen atoms and the surface-state density is greatly reduced. Surface recombination is a nonequilibrium carrier recombination process. We have shown previously that there are “deep-levels” on the surface, similar to those in the bulk through which nonequilibrium carriers can recombine. The recombination rate through these surface energy levels is according to an extension of the S–R theory: .n0 C p0 /p (3.157) Uz D n C n ps0 C ps1 : s0 s1 C NST cp NST cn Surface recombination rate is: SD

Uz .n0 C p0 / D n Cn ps0 C ps1 : s0 s1 p C Sp Sn

(3.158)

The surface recombination rate of a hole is: Sp D p vp NsT :

(3.159)

186

3 Recombination

Fig. 3.49 The space charge area distribution of an n-type semiconductor

The surface recombination rate of an electron is: Sn D n vn NsT :

(3.160)

Hence, we have: SD

p n vp vn NsT .n0 C p0 / : n vn .ns0 C ns1 / C p vp .ps0 C ps1 /

(3.161)

Figure 3.49 shows a trap energy level, ET , at the surface of an n-type semiconductor, in which EC is the conduction band minimum, EV the valance band maximum, EF the Fermi energy, VS the maximum of the surface-potential band bending at the conductive band edge. Under the thermal equilibrium condition, and if the electric current due to the recombination of surface electrons and holes is small, then the bulk and surface can be considered to be in an equilibrium state, so we get:  n.z/ D ni exp and

eV .z/ EF  E T C kB T kB T



  EF  ET eV .z/ p.z/ D ni exp   : kB T kB T

(3.162)

(3.163)

Now, supposing that: us D ub C vs D

eV .z/ EF  ET C ; kB T kB T

(3.164)

we find: n0 D ni exp.ub /; p0 D ni exp.ub /;

(3.165) (3.166)

ns0 D ni exp.us / D n0 exp.eVs =kB T /; ns0 D ni exp.us / D n0 exp.eVs =kB T /:

(3.167) (3.168)

3.6 Surface Recombination

187

Let, u0 ln.p vp =n vn /=2, then: p n vp vn NsT .n0 C p0 / h i 9  S D 8 F = < n vn ni exp.ub C vs / C exp EkT E BT h i  :C v n exp.u  v / C exp EF ET ; p p i b s kB T D

p p n vp vn NsT .n0 C p0 / i  T 2ni cosh.us  u0 / C cosh EkF E  u 0 BT

(3.169)

p p n vp vn NsT .n0 C p0 /    : EF  ET  u0 2ni 1 C cosh kB T

(3.170)

h

and Smax D

To deduce a value for S , we first must know NsT , and second the energy ET . Figures 3.50 and 3.51 are sketches of Smax . From this figure, we find that the value of Smax lies in the range 102 –104 cm=s. Therefore, we have:   EF  E T  u0 1 C cosh S kB T :  D (3.171) EF  E T Smax  u0 cosh.us  u0 / C cosh kB T In an oxidized surface layer on HgCdTe, various kinds of charge states will appear. Due to the high density of fixed charge in HgCdTe, a detailed analysis of surface charge and surface potential is needed. Related computations (Gong 1993) ˚ the rate of indicated that when the thickness of an oxidized layer is about 700 A, surface recombination is a minimum. Because the high fixed charge density (Qfc is in the range of 5  1011  1  1012 cm2 (Nemirovsky 1990)) in the surfaceoxidized layer, the surface energy band of HgCdTe is seriously bent downward, this

Fig. 3.50 Relation between Smax and temperature T

188

3 Recombination

Fig. 3.51 The relation between S=Smax and us  u0

means Vs is very large. Meanwhile, the forbidden band of HgCdTe is very narrow, so degenerate states readily appear at the surface, thus Boltzmann distributions must be replaced by Fermi distributions. In addition, similar to the bulk situation, both Auger recombination and radiative recombination must be included. Experimental lifetimes should actually be a comprehensive result of surface recombination and bulk recombination. If the two kinds of recombination processes do not influence each other, the effective lifetime of a nonequilibrium carrier will be: 1 D 1B C 1s .

3.6.2 Surface Recombination Rate In the measurement of lifetimes, especially the measurement of the intensity variation of light-generated carriers, we must distinguish between the relative contributions of surface recombination and bulk recombination. During the measurement process, the light should be carefully regulated to be quasi-monochromatic and have a low intensity, to prevent the creation of a high density of electron–hole pairs and a heavily nonuniform carrier distribution in the surface area. In this case, the surface recombination current density can be expressed as eSıp, here ıp is the density of surplus minority carriers near the surface, and S is a surface recombination rate constant with the unit cm/s. Given these conditions, the observed lifetime can be expressed as: 1

obs

D

1 1 C ;

B

s

(3.172)

in which s is the surface recombination lifetime and B is the bulk recombination lifetime. These two times constants can be distinguished, in principle, through experiments (including a change of a sample’s cross sectional size). If the object

3.6 Surface Recombination

189

studied has a rectangular-cross-section .2A  2B/, and the carriers are uniformly generated, Shockley (1950) pointed out that the relation between s and S , the recombination rate per unit volume, can be expressed as: 1 DD

S



2 2 C 2 2 A B

 ;

(3.173)

where D is the minority carrier diffusion constant, SA=D  tan , and SB=D

 tan . The pair of smallest solutions of these equations, 0 and 0 , correspond to the longest lifetime, and set an important limit. After carefully washing and etching, the surface recombination rates for germanium and silicon can be reduced to values lower than 103 cm=s, while that of compound semiconductors can be reduced to values lower than 105 cm=s. Now, let’s investigate an n-type semiconductor material. Suppose the surface area contains a uniform recombination center density Nr per unit area, with all the centers located at the Ei -es energy level (Ei is the energy of the gap’s center). These energy states will often accept electrons, and produce a depletion layer near the surface, as shown in Fig. 3.52. The recombination rate due to this kind of recombination center is determined by its capture cross-section and the acquisition rates of surface holes and electrons. When the hole and electron distribution is nondegenerate, we can get a recombination rate per unit area from a statistical analysis: rs D

Nr cp cn .pb C nb /ıp : cp .ps C ps1 / C cn .ns C ns1 /

(3.174)

In this equation cp and cn are, respectively, the probability per unit time and volume of a hole or an electron being captured by the recombination center, given by the

Fig. 3.52 Acceptor-like surface states below the mid-gap for an n-type semiconductor

190

3 Recombination

product of corresponding capture cross-section and the velocities of their thermal motion; ps and ns are densities of free carriers on the surface; ps1 and ns1 are surface densities when the Fermi energy is at the energy Ei . pb and nb are densities of bulk carriers, ıp is density of surplus minority carriers inside surface space charge layer. Supposing the densities ps and ns equal those of the bulk, then, according to (3.174), the surface recombination rate is given by: sD

rs D ıp

Nr cp cn .pb C nb /   ; (3.175)  EF  Ei C e's EF  Ei C e's C ni cp exp  ni cn exp kB T kB T 

es is negative if the level es lies bellow the center of the gap. According to the Shockley–Read–Hall (Shockley and Read 1952; Hall 1952) discussion, the above formula applies to a recombination center having a singleenergy-level. Gr¨afe (1971) has studied the validity of the above formula. Because the formula is a simple model of an extremely complicated situation, it can be only accepted to a certain extent.

3.6.3 The Effect of Fixed Surface Charge on the Performance of HgCdTe Photoconductive Detectors Passivation technology in the fabricating of Hg1x Cdx Te photoconductive detectors are designed to form heavy accumulated layers at the surfaces of Hg1x Cdx Te. Accumulated layers will reduce the surface recombination rate and improve the device performance; on the other hand, due to its area of high conductance, the resistance, and further, the responsivity and detectivity of the device are degraded. Therefore, a theoretically optimized passivation treatment of devices can guide the direction for improving device performance. The importance of the passivation layer was noted early (Kinch 1981), and further investigations were reported (Nemirovsky and Bahir 1989; Nemirovsky 1990). An accumulated layer caused by passivation technology obviously has a two-dimension character. We can adopt Fang–Howard’s variational method (Fang and Howard 1966) to calculate the distribution of the surface potential in a onedimension model to calculate the distribution of light-induced carriers and their voltage response in a Hg1x Cdx Te photoconductive detector. A large amount of fixed positive charge exists in the passivation layer on a Hg1x Cdx Te photoconductive detector, which can induce an equal density of electrons on the surface of a bulk material. These surface electrons distribute within a very thin thickness to form a quasi-two-dimensional electron gas. Many theoretical methods have been developed to calculate the properties of a two-dimensional electron gas, and models have been developed already for a single band and for multi-bands. Poisson and Schr¨odinger equations are the start of all these models. A variational self-consistent method developed by Fang and Howard is a relatively

3.6 Surface Recombination

191

simple and practical method. In Fang’s model, the density of surface electrons is assumed to be much higher than that of the bulk-electron density; therefore, the surface potential and the density of fixed positive charges in the surface have the following relation: 3NI e 2 ; (3.176) VH D 2"s "0 b where

 bD

33mn e 2 NI 8"s "0 „2

 :

(3.177)

Here, mn is the effective mass of the electrons, e the charge of an electron, "0 and "s are the vacuum dielectric constant and the low-frequency dielectric constant. Lowfrequency dielectric constants (Yadava et al. 1994) have been related to the material composition: "s D 20:8  16:8x C 10:6x 2  9:4x 3 C 5:3x 4 :

(3.178)

This surface potential arising from the accumulated layer in HgCdTe will prevent holes from moving toward the surface. In this case, the rate of the effective surface recombination (White 1981) is: Seff D S0 exp.VH =kB T /;

(3.179)

where S0 is the surface recombination rate in a flat band situation, kB the Boltzmann constant, and T is the temperature. Accumulated layers exist in both the top and bottom surfaces in a HgCdTe photoconductive detector, assuming the top and bottom surfaces are identical, then the resistance of the detector is: RD

1 1 : .Nb b C 2NI s =d /e wd

(3.180)

Here, l, w, and d are the length, width, and height of detector, respectively, Nb the bulk electron density, s mobility of the surface electrons (about 104 cm2 =Vs at 77 K), and b is the mobility of the bulk electrons which can be expressed by Rosbeck’s formula (Rosbeck et al. 1982). For a Hg1x Cdx Te material with a composition of x D 0:2, b is about 1–3  105 cm2 =Vs at 77 K. This surface recombination has important influence on the lifetime of minority carriers. Because of the existence of surface recombination, the real lifetime of material with bulk lifetime b becomes: 1= net D 1= b C 1= s D 1= b C 2Seff =d:

(3.181)

Equation (3.183) captures the influence of the surface potential on the surface recombination rate. To calculate the real lifetime, we have adopted the effective surface recombination rate given in (3.181).

192

3 Recombination

For photoconductive detector operating under constant current model, the voltage response to monochromatic radiation (wavelength D ) is: RV D .= hc/qR.b E net = l/:

(3.182)

In which, E is the intensity of the bias electric field, c the velocity of light, h the Plank constant,  the quantum efficiency,  the wavelength, the R on the left is the voltage responsivity RV , and the R on the right is the resistance. In order to study the influence of surface fixed charge on the performance of a device (only the situation in which T D 77 K is considered), we suppose the material for fabricating the photoconductive detector is n-type, the composition is x D 0:214, the bulk lifetime of minority carriers is 10 ns to 10 s, the concentration of impurities is 5  1014 to 5  1015 cm3 , and the mobility of surface electrons is 2  104 cm2 =Vs. The photosensitive area of the detector is 50  50 m, and the thickness is 88 m. The wavelength of incident light is 10:6 m, quantum efficiency is 0.6, and the bias electric field is 20 V/cm. The relation of the detector resistance and surface fixed charge is shown in Fig. 3.53. The electron accumulated layer at surface caused by passivation is a high-conductance leakage path, and it will reduce the resistance of the device and deteriorate its performance. It can be seen from Fig. 3.53 that when the density of surface fixed positive charges changes between 1011 and 1012 cm2 , the functional relation between the surface fixed charge and the resistance of a detector changes dramatically. If NI < 1011 cm2 , the resistance of the detector is mainly decided by that of the bulk material and is nearly independent of the surface passivation; while for the case of NI > 1012 cm2 , the resistance of the detector is mainly due to the density of surface electrons caused by the surface passivation.

Fig. 3.53 Relation between the resistance R of devices which have different bulk carrier densities and the density NI of surface fixed electric charges

3.6 Surface Recombination

193

Fig. 3.54 Relations between the net lifetime net of devices, that have difference surface recombination rates S0 , and the density of surface fixed electric charge NI

The effect of surface fixed charges on the net lifetime net of a detector is shown in Fig. 3.54. When NI is very small, net is also short and it increases rapidly with an increase of NI until it reaches b . An electron accumulated layer is formed in the surface region of an n-type detector due to the surface fixed charge, causing an energy band bending at the surface. This forms a potential well for electrons, which serves as a barrier for bulk minority carriers (holes), thus preventing the lightgenerated holes from diffusing to surface and recombining. Therefore, the existence of surface accumulated layer reduces the surface recombination rate. The repulsive surface potential for holes increases with an increase of the density of fixed charge, as described by (3.178). When the density of fixed charge exceeds 3  1011 cm2 , the surface potential barrier to holes becomes high enough to prevent light-generated holes from passing through it to reach the detector surface, even for surface recombination rates as high as 1  105 cm=s. This phenomenon is very favorable to the improvement of detector performance. The relations between the voltage responsivity and the density of fixed charge for different doping concentrations of bulk material are shown in Fig. 3.55. The lifetime of minority carriers in these detectors is 1 s, and the surface recombination rate is 1;000 cm=s, which means these are high-efficiency devices. When the density of fixed charges in the passivation layers exceeds 1011 cm2 , the existence of surface barriers reduces the recombination loss of light-generated holes, and the performance of devices is improved. Once the densities of fixed charges exceed 1012 cm2 , the increase of the conductivity due to the surface accumulate layer leads to a decrease of the intrinsic resistance and the performance of devices. With a further increase of the density of fixed charge, the performance drops quickly, especially for lightly doped devices.

194

3 Recombination

Fig. 3.55 Relations between voltage responsivity Rv of devices that have different doping densities Nb , and the density of surface fixed electric charge NI

Fig. 3.56 Relations between voltage responsivity Rv of devices that have different surface recombination rates S0 , and the density of fixed electric surface charge NI

The relation between the voltage responsivity and the density of fixed charge for different surface recombination rates are shown Fig. 3.56. When the lifetime of minority carriers in a device is 1 s, and the doping concentration of the bulk material is 5  1014 cm3 , the voltage responsivity has a peak value when the density of fixed charge lies in the range of 1011 –1012 cm2 . As the surface recombination rate increases, the peak shifts toward a higher density of fixed charge. The height of the peak is determined by the surface recombination rate. The lower the surface recombination rate, the higher is the voltage responsivity. When the density of fixed charge is higher than 6  1011 cm2 , the performance of detectors is insensitive to the surface recombination rate, even though the surface recombination rate changes

3.6 Surface Recombination

195

Fig. 3.57 Relation between voltage respond Rv of device which have different lifetime b of few carriers and the density of surface fixed electric charge NI

by two orders of magnitude. This indicates that by choosing an appropriate passivation technology, we can control the effective surface recombination rate and improve device performance. The relation between the voltage responsivity and the density of fixed charge for different minority carrier lifetimes is shown in Fig. 3.57. In these calculations, the bulk material doping concentration is taken to be 5  1014 cm3 , and the surface recombination rate is 105 cm=s. In this situation, if the density of the surface-fixed charge is lower than 1011 cm2 , due to the fact that the effective lifetime net of a device is mainly determined by the surface recombination rate, the performance of devices is basically independent of the minority carrier lifetime. The performance of detectors changes greatly when the density of surface-fixed charges lies in the range of 1011 –1012 cm2 . This is especially true for long-lifetime devices ( b D 10 s), where the detector voltage responsivity changes by over two orders of magnitude for a small change in Ni . According to the above discussion, we know that the performance of HgCdTe photoconductive detector is highly related to the density of surface-fixed charge caused by passivation technology. The existence of surface-fixed charge can reduce the loss of light-generated holes by surface recombination and improve the performance of the device, on the other hand, it will reduce the performance of the device by reducing the resistance of the device, these two aspects are contradictory to each other. In other words, we can optimize the performance of the device by choosing appropriate passivation technology to control the density of surface-fixed charge.

196

3 Recombination

Appendix 3.A The results of (3.69) and (3.70) can be also obtained from the Fermi level distribution analysis. Equations (3.64) and (3.65) can be written as: n 1 D n0

1  fT0 fT0

(3.a.1)

p1 D p 0

fT0 ; 1  fT0

(3.a.2)

and

where fT is given by (3.60). Then, we can get: NT D NT fT Š NT fT0 NT0 D NT .1  fT / Š NT .1  fT0 /:

(3.a.3)

Equation (3.a.3) is well approximated in (3.66) and (3.67) because their equilibrium values are never far from equilibrium. Now, we treat three simple cases: .a/

EF  E T  1: kT

In this case, generally the material is n-type, we have fT0 Š 1, 1  fT0 Š 0, Š 0. Due to p1 NT0 D NT0 Š 0, and n1 NT Š 0. Then, (3.66) reduced to dn dt 0

 f Š cp NT .p  p0 /. Its solution p0 1fT 0 NT 1  fT0 Š p0 NT , (3.67) becomes dp dt T for the S–R relaxation time is given by: 1

Sa–R Š p vp NT ;

(3.a.4)

where p is the hole capture cross section, and vp is the speed of a hole. Sa–R is limited by the relaxation of the hole concentration. For an n-type material there is a larger chance the traps will first capture more electrons and then capture holes to assist the recombination. So, the lifetime is determined by the hole-capture crosssection and velocity. .b/ ET D EF 

In this case, we have fT0 D 1  fT0 D 12 , NT0 D NT D N2T , n1 D n0 , and p1 D p0 . Then, (3.66) and (3.67) become: dn NT .n  n0 / ; Š cn dt 2

(3.a.5)

Appendix 3.B Sandiford Paper

197

dp NT .p  p0 / : Š cp dt 2

(3.a.6)

bp

There are two S–R relaxation times ( Sbn–R and S–R ) associated with the solutions to (3.a.5) and (3.a.6). The solutions are given by

Sbn–R D 2 .n vn NT /1 ; 1

bp ;

S–R Š 2 p vp NT

(3.a.7) (3.a.8)

where n is the electron capture cross-section, and vn is the speed of electron. In any bp case, the time constant, due to the factor of 2, Sbn–R or S–R is likely to be longer than the minimum S–R relaxation time and it occurs when ET D EF . .c/

ET  EF  1: kT

In this case, generally the material is p-type, we have fT0 Š 0, 1fT0 Š 1, n1 NT Š n0 NT , p1 NT0 Š 0. Then, (3.66) and (3.67) become: dn Š cn NT .n  n0 / ; dt dp Š 0: dt The solution is given by

Sc–R Š .n vn NT /1 :

(3.a.9) (3.a.10)

(3.a.11)

Sc–R is limited by the relaxation of the electron concentration. For a p-type material there is a smaller chance an electron will be captured but once it is the hole will be captured quickly to assist the recombination. So, the lifetime is determined by the electron capture cross-section and velocity.

Appendix 3.B Sandiford Paper He writes the continuity equations in the form (notation adjusted to agree with that used in this book): 

 dp D cp NT C p0 C p1 p  cp .p0 C p1 / n; dt

(3.b.1)



 dn D cn NT0 C n0 C n1 n  cn .n0 C n1 / p: dt

(3.b.2)

198

3 Recombination

Next, take the derivative of (3.b.1) with respect to time and substitute (3.b.2) for dn , and then substitute for n from (3.b.1). The result is: dt d2 p dp C G2 p D 0; C G1 2 dt dt

(3.b.3)

where



 G1 cp NT C p0 C p1 C cn NT0 C n0 C n1 and



  (3.b.4) G2 cn cp NT C p0 C p1 NT0 C n0 C n1  .p0 C p1 / .n0 C n1 / : Note (3.b.3) is homogeneous and has a solution: p D Ae HC t C Be H t ;

(3.b.5)

in agreement with Eq. 4 of Sandiford (1957). The solutions for H are:

H˙ D

G1 ˙

q

G12  4G2 2

:

(3.b.6)

The corrected version of Sandiford’s Eq. 5 (Sandiford 1957) is: G12  4G2

(3.b.7)

In this approximation, we find: HC Š G1 and H Š

G2 : G1

(3.b.8)

From the initial conditions, we have: A C B D p .0/ ; and HC A C H B D G3 ;

(3.b.9)

where G3 cp Œ.po C p1 / .p .0/  n .0//  NT p .0/:

(3.b.10)

The solutions to (3.b.9) are: A D p .0/  B and B D

G3  HC p .0/ : H  HC

(3.b.11)

References

199

A number of special cases can be treated. Suppose an n-type semiconductor with, .ET  EF /=kB T > 1, so n1 > n0  p0 > p1 , and photo excitation so p .0/ D n .0/. Then, we find: A Š 0 and B Š p .0/ : (3.b.12) so p .t / Š p .0/ e t= ;

(3.b.13)

1 cp N  :

(3.b.14)

where Thus in this case B >> A and the observed decay is the slow response corresponding to H not the fast decay due to HC . This contrasts with the conclusion drawn by Sandiford. This whole treatment only applies to the approximation where NT and NT0 are taken to be independent of time, and hence does not correspond the real situation. However, it is a generalization of the treatment in Appendix 3.A where the populations of the trap states are taken to remain constant while the system relaxes. All three cases (a), (b), and (c) can be done. This is essentially case (a).

References Adomaitis E, Grigoras K, Krotkus A (1990) Minority carrier recombination in p-type Cdx Hg1-x Te. Semicond Sci Technol 5:836–841 Afromowitz MA, Didomenico M (1971) Measurement of free-carrier lifetimes in GaP by photoinduced modulation of infrared absorption. J Appl Phys 42:3205–3208 Baars J, Sorger F (1972) Reststrahlen spectra of HgTe and Cdx Hg1x Te. Solid State Commun 10:875–878 Baicker JA, Fang PH (1972) Transient conductivity of silicon. J Appl Phys 43:125–131 Bajaj J, Babulac LO, Newman PR, Tennant WE (1987) Spatial mapping of electrically active defects in HgCdTe using laser beam-induced current. J Vac Sci Technol A 5:3186–3189 Baker IM, Capocci FA, Charlton DE, Wotherspoon JTM (1978) Recombination in cadmium mercury telluride photodetectors. Solid State Electron 21:1475–1480 Bardeen J, Blatt FJ, Hall LH (1956) In: Breckenridge RC (ed) Photoconductivity Conference, Atlantic City 1954. Wiley, New York Bartoli F, Allen R, Esterowitz L, Kruer M (1974) Auger-limited carrier lifetimes in HgCdTe at high excess carrier concentrations. J Appl Phys 45:2150–2154 Beattie AR (1962) Quantum efficiency in InSb. J Phys Chem Solids 23:1049–1056 Beattie AR, Landsberg PT (1959) Auger effect in semiconductors. Proc R Soc London Ser A 249:16–29 Beattie AR, Smith G (1967) Recombination in semiconductors by a light hole Auger transition. Phys Status Solidi 19:577–586 Blakemore JS (1962) Semiconductor Statistics. Pergamon, Oxford Casselman TN (1981) Calculation of the Auger lifetime in p-type Hg1-x Cdx Te. J Appl Phys 52:848–854 Casselman TN, Petersen PE (1980) A comparison of the dominant Auger transitions in ptype (Hg,Cd)Te. Solid State Commun 33:615–619 Chen JS, Bajaj J, Tennant WE, Lo DS, Brown M (1987) On the Auger recombination process in p-type LPE HgCdTe. IN: Materials for infrared detectors and sources; Proceedings of the Symposium, Boston, MA, 1986. Materials Research Society, Pittsburgh, PA, pp 287–293

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Chen MC, Colombo L (1992) Minority-carrier lifetime in indium-doped n-type Hg0:78 Cd0:22 Te liquid-phase-epitaxial films. J Appl Phys 72:4761–4766 Chen MC, Colombo L, Dodge JA, Tregilgas JH (1995) The minority carrier lifetime in doped and undoped p-type Hg0:78 Cd0:22 Te liquid phase epitaxy films. J Electronic Materials 24:539–544 Choo SC (1970) Carrier lifetimes in semiconductors with two interacting or two Independent recombination levels. Phys Rev B 1:687–696 Chu JH, Sher A (2007) Physics and Properties of Narrow Gap Semi-Conductors. Springer, New York Chu JH, Xu SQ, Tang DY (1982) Chinese Sci. Bull 27:403 Chu JH, Xu SQ, Tang DY (1983) Energy gap versus alloy composition and temperature in Hg1-x Cdx Te. Appl Phys Lett 43:1064–1066 Chu JH, Li B, Liu K, Tang DY (1994) Empirical rule of intrinsic absorption spectroscopy in Hg1-x Cdx Te. J Appl Phys 75:1234–1235 Elliott CT (1977) Pat. 1488258 Elliott CT (1981) New detector for thermal imaging systems. Electron Lett 17:312–313 Fang FF, Howard WE (1966) Negative field-effect mobility on (100) Si surfaces. Phys Rev Lett 16:797–799 Gerhardts RR, Dornhaus R, Nimtz G (1978) The Auger-effect in Hg1-x Cdx Te. Solid State Electron 21:1467–1470 Gong HM (1993) PhD thesis, Shanghai Institute of Technical Physics Gr¨afe W (1971) Extension of the surface recombination model and unique determination of the recombination energy by means of reverse current measurements. Phys Status Solidi A 4: 655–662 Hall RN (1952) Electron-hole recombination in Germanium. Phys Rev 87:387–387 Hall RN (1959) Proc Inst Electr Eng B Suppl 106:923 Hovel HJ (1992) Scanned photoluminescence of semiconductors. Semicond Sci Technol 7:A1–A9 Huang QS, Tang DY (1965) Recombination processes of carriers in Indium antimonide. Acta Phys Sin 21:1038 Jones CL, Capper P, Gosney JJ (1982) Thermal modelling of bridgman crystal growth. J Crystal Growth 56:581–590 Kinch MA (1981) In: Willardson RK, Beer AC (eds) Semiconductor and Semimetal, Vol. 18. Academic, New York, p 287 Kinch MA, Brau MJ, Simmons A (1973) Recombination mechanisms in 8–14- HgCdTe. J Appl Phys 44:1649–1663 Kopanski JJ, Lowney JR, Novotny DB, Seiler DG, Simmons A, Ramsey J (1992) High-spatialresolution resistivity mapping applied to mercury cadmium telluride. J Vac Sci Technol B 10:1553–1559 Krishnamurthy S, Berding MA, Yu ZG (2006) Minority Carrier Lifetimes in HgCdTe Alloys J of Elect Materials 35:1369–1378 Kurnick SW, Powell JM (1959) Optical absorption in pure single crystal InSb at 298ı and 78ı K. Phys Rev 116:597–604 Lacklison DE, Capper P (1987) Minority carrier lifetime in doped and undoped ptype Cdx Hg1-x Te. Semicond Sci Technol 2:33–43 Ling ZG, Lu PD (1984) Chinese J Semicond 5:144 Long D, Schmit JL (1970) In: Willardson RK, Beer AC (eds) Semiconductor and Semimetal, Vol. 5, Chapter 5. Academic, New York Many A, Goldstein Y, Grover NB (1965) Semiconductor Surfaces. Willey, New York Mao WY, Chu JH (1993) J Infrared MilliWaves 13:352 Milnes AG (1973) Deep impurities in semiconductors. Wiley, New York Mooradian A, Fan HY (1966) Recombination Emission in InSb. Phys Rev 148:873–885 Moss TS, Burrell GJ, Ellis B (1973) Semiconductors Opto-electronics. Buttorworth, London, p 38 Mroczkowski JA, Shanley JF, Reine MB, LoVechio P, Polla DL (1981) Lifetime measurement in Hg0:7 Cd0:3 Te by population modulation. Appl Phys Lett 38:261–263 Nemirovsky Y (1990) Passivation of II-IV compounds. J Vac Sci Technol A 8:1185–1187

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Nemirovsky Y, Bahir G (1989) Passivation of mercury cadmium telluride surfaces. J Vac Sci Technol A 7:450–459 Petersen PE (1970) Auger Recombination in Hg1-x Cdx Te. J Appl Phys 41:3465–3467 Pines MY, Stafsudd OM (1980) Recombination process in intrinsic semiconductors using impact ionization capture cross sections in indium antimonide and mercury cadmium telluride. Infrared Phys 20:73 Polla DL, Tobin SP, Reine MB, Sood AK (1981a) Experimental determination of minority-carrier lifetime and recombination mechanisms in p-type Hg1-x Cdx Te. J Appl Phys 52:5182–5194 Polla DL, et al. (1981b) Proceeding of the 4th International Conference on the Physics of Narrow Gap Semiconductors. Linz, Austria, p 153 Pratt RG, Hewett J, Capper P, Jones CL, Quelch MJ (1983) Minority carrier lifetime in n-type Bridgman grown Hg1-x Cdx Te. J Appl Phys 54:5152–5157 Roosbroeck W, Shockley W (1954) Photon-Radiative Recombination of Electrons and Holes in Germanium. Phys Rev 94:1558–1560 Rosbeck JP, Starr RE, Price SL, Riley KJ (1982) Background and temperature dependent currentvoltage characteristics of HgCdTe photodiodes. J Appl Phys 53:6430–6440 Sah CT, Tasch AF Jr (1967) Precise Determination of the Multiphonon and Photon Carrier Generation Properties using the Impurity Photovoltaic Effect in Semiconductors. Phys Rev Lett 19:69–71 Sandiford DJ (1957) Carrier Lifetime in Semiconductors for Transient Conditions. Phys Rev 105:524–524 Schacham SE, Finkman E (1985) Recombination mechanisms in p-type HgCdTe: Freezeout and background flux effects. J Appl Phys 57:2001–2009 Schiff L (1955) Quantum Mechanics. McGraw-Hill, New York Schmit JL (1970) Intrinsic Carrier Concentration of Hg1-x Cdx Te as a Function of x and T Using kp Calculations. J Appl Phys 41:2876–2879 Shockley W (1950) Energy band structures in semiconductors. Phys Rev 78:173–174 Shockley W (1958) Electrons, holes, and traps. Proc IRE 46:973–990 Shockley W, Read WT (1952) Statistics of the recombinations of holes and electrons. Phys Rev 87:835–842 Souza ME de, Boukerche M, Faurie JP (1990). Minority-carrier lifetime in p-type (111)B HgCdTe grown by molecular-beam epitaxy. J Appl Phys, 68:5195–5199 Srour JR, Curtis OL (1972) Techniques for obtaining recombination-center parameters from carrier lifetime studies. J Appl Phys 43:1779–1784 Staszewski GM von, Wollrab R (1989) Role of nC-accumulation layers on the carrier lifetime of n-Hg1-x Cdx Te. SPIE 1106:110 Tamm IE (1932) A possible kind of electron binding on crystal surfaces. Physikalische Zeitschrift der Sowjetunion 1:733–746 Tang DY (1974) Infrared Phys Technol 16:345 Tang DY (1976) Infrared Phys Technol 25–26:53 Tung T, Kalisher MH, Stevens AP, Herning PE (1987) Liquid-phase epitaxy of Hg1-x Cdx Te from Hg solution – A route to infrared detector structures. Mat Res Soc Symp Proc Vol. 90. Mater Res Soc, Pittsburg, p 321 Wertheim GK (1958) Transient recombination of excess carriers in semiconductors. Phys Rev 109:1086–1091 White AM (1981) The influence of surface properties on minority carrier lifetime and sheet conductance in semiconductors. J Phys D: Appl Phys 14:L1–L3 Wijewarnasuriya PS, Lange MD, Sivananthan S, Faurie JP (1995) Minority carrier lifetime in Indium-doped HgCdTe (211)B epitaxial layers grown by molecular beam epitaxy. J Electronic Materials 24:545–549 Yadava RDS, Gupta AK, Warrior AVR (1994) Hole scattering mechanisms in Hg1-x Cdx Te. J Electron Mater 23:1359–1364

Chapter 4

Two-Dimensional Surface Electron Gas

4.1 MIS Structure 4.1.1 The Classical Theory of an MIS Device The simplest metal-insulator-semiconductor device structure, shown in Fig. 4.1, includes a metal gate, an insulator layer on a semiconductor surface, and a back metal ohmic contact. tox is the thickness of insulator and "ox is its dielectric constant. The insulator layer lies between the metal gate and the top semiconductor surface. A bias voltage is applied to the metal gate to control the surface potential of the semiconductor surface. When the bias voltage reaches a threshold, the ntype semiconductor becomes strongly inverted. The resulting energy band bending is shown in Fig. 4.2. The potential ˚ as a function of displacement x from semiconductor surface is obtained from the one-dimensional Poisson equation. Under nondegenerate and thermal equilibrium conditions, we have: i q h d2  q =kB T q =kB T n D  .e  1/  p .e  1/ : n0 n0 dx 2 ""0

(4.1)

The electrical field distribution is ED

  2kB T 1=2 d D˙ F ./; dx ""0

(4.2)

where  1=2    q q q =kB T q =kB T  1 C pn0 e 1  C ; (4.3) F ./ D nn0 e kT kT and nn0 and pn0 are the concentrations of majority and minority carriers in the semiconductor, " is its permittivity, and q is the magnitude of the electron charge. From Gauss’s law, the space charge per unit area in a semiconductor required to produce this field is Qs D ""0 Es D ˙.2""0 kB T /1=2 F ./: J. Chu and A. Sher, Device Physics of Narrow Gap Semiconductors, Microdevices, c Springer Science+Business Media, LLC 2010 DOI 10.1007/978-1-4419-1040-0 4, 

(4.4) 203

204

4 Two-Dimensional Surface Electron Gas

Fig. 4.1 The simplest metalinsulator-semiconductor device structure

Fig. 4.2 The energy band diagram of an MIS device when the bias voltage reaches a threshold where the n-type semiconductor becomes strongly inverted

A typical variation of the space-charge density Qs as a function of the surface potential 's is shown in Fig. 4.3 for a typical n-type HgCdTe detector .n0 D 2  1015 cm3 / with a cutoff wavelength of c D 5 m, at 77 K. Note that for a positive 's , Qs corresponds to accumulation. The function F .'/ is dominated by the first term in (4.3), that is, Qs  exp.qs =2kB T /. For 's D 0, we have the flat-band condition and Qs D 0. For negative 's , the function F .'/ is now dominated by the second term, that is, Qs  j's j1=2 . The space charge of a semiconductor is determined by ionized impurities in the depletion layer of the semiconductor. For 's << 0, the concentration of minority carriers on the semiconductor surface will be much larger than the concentration of bulk majority carriers; the function F .'/ is now dominated by the fourth term, that is, Qs  exp.qjs j=2kB T /. For j's j > j2'F j, strong inversion begins, and the surface potential is:     nn0 kB T ln (4.5) sinv D 2F D  q pn0 or

  q inv D ps ; nn0 D pn0 exp  s kB T

where 'F is the bulk Fermi potential shown in Fig. 4.2, and ps is the surface concentration of minority carriers.

4.1 MIS Structure

205

Fig. 4.3 A typical variation of the space-charge density Qs as a function of the surface potential s for an n-type semiconductor

The differential capacitance of the semiconductor space charge layer is given by: # 1=2 "  @Qs ""0 q 2 nn0 .e q =kB T  1/  pn0 .e q =kB T  1/ Cd

D : @s 2kB T F ./

(4.6)

Similarly, for 's > 0, corresponding to the accumulation region,(4.6) can be approximated by Cacc / exp.qs =2kB T /. And then, for 's > several .kB T =q/, the capacitance of the semiconductor space charge layer will be large. In the strong inversion case, (4.6) can be approximated by Cinv / exp.qjs j=2kB T /. Similarly, for j's j > several.kB T =q/, the capacitance of the strong inversion region will be large. For surface potentials 's in the depletion region and the weak inversion region, the space charge capacitance is determined by the depletion layer of the semiconductor. Equation (4.6) can be approximated by Cd D .""0 qN=2's /1=2 . This is the depletion layer capacitance, Cd D ""0 =W , where W is width of the depletion layer, as shown in Fig. 4.2. In an ideal strongly inverted MIS device, the inversion layer can be regarded as a layer with charge Qinv and with a width approaching zero, and the depletion layer can be regarded as a region populated by intrinsic carriers. An applied voltage VG

206

4 Two-Dimensional Surface Electron Gas

will partly appear across the insulator and partly across the space charge layer. Thus, by Gauss’s law, we have: "ox "0

VG  's D Qinv C qNW; tox

(4.7)

where N is net impurity concentration of the depletion layer with thickness W , and tox is the thickness of the oxide insulator layer. The surface potential related to the applied voltage is given by (Macdonald 1964): 's D VG0 C V0  .2VG0 V0 C VG2 /1=2 ;

(4.8)

2 , Cox D "ox "0 =tox , and where VG0 D .VG  VFB / C .Qinv =Cox /, V0 D qN ""0 =Cox VFB is the flat band voltage of the device. The total capacitance of an ideal MIS device is a series combination of the insulator capacitance Cox and the semiconductor space charge layer capacitance Cd :

C D

Cox Cd .Cox C Cd /

(4.9)

The capacitance Cd given by (4.6) depends on the voltage. Then from (4.9), we can find a relation between C and VG . For an ideal MIS device .VFB D 0/, the theoretical variation of the C curve with VG is shown in Fig. 4.4. The device parameters (n-HgCdTe) used are Eg  0:25 eV, and n0 D 1015 cm3 . At a positive voltage, we have an accumulation of electrons and therefore a high differential capacitance .Cd D Cacc / of the semiconductor. As a result, the total capacitance is close to the insulator capacitance Cox . When the voltage becomes sufficiently negative, 's < 0, and forms a depletion region acting as a dielectric in

Fig. 4.4 Theoretical variation of low- and high-frequency capacitance curves with VG for an n-HgCdTe .Eg D 0:25 eV/ at 77 K (Chapman et al. 1978)

4.1 MIS Structure

207

series with the insulator, the total capacitance .Cd D .""0 qN=2's /1=2 / decreases. When the negative voltage is farther reduced, the capacitance goes through a minimum .Cmin / and then increases again as an inversion layer of electrons forms at the surface. The differential capacitance of the semiconductor space charge layer .Cd D Cinv / again approaches Cox with a sufficient reduction of the negative voltage. This curve is a low-frequency capacitance spectrum. The above theory depends on the ability of the carriers to follow the applied ac voltage. It is possible in the accumulation layer and depletion layer. However, in the inversion layer, the minority carriers cannot keep up with a rapidly varying applied voltage. The carriers have a characteristic response time required to follow an applied ac voltage. The response time depends on the concentration of the effective minority carriers in the surface region. In the inversion layer, the response time of the minority carriers is inversely proportional to their induced dark current. At sufficiently high frequencies, the concentration of effective carriers in the inversion layer will change with the applied ac signal but cannot keep pace with it. The resulting curve is the high-frequency capacitance spectrum. The capacitance limit is Cox Cd =.Cox C Cd /. This constitutes a finite capacitance that joins the majority and the minority carriers region. In Fig. 4.4, the curve marked “pulsed” shows the capacitance curve of an MIS device response to high frequencies. When the frequency of a bias voltage is high enough, the minority carriers cannot respond at the semiconductor surface in time, and a deep depletion region is formed in the device. The total capacitance measured is equal to a series combination of Cox and Cd , where Cd D .""0 qN=2's /1=2 is the capacitance of the depletion layer and 's is determined by (4.8). Figure 4.4 does take into account the effect of degenerate and nonparabolic bands, VG is large and positive, so the value of the accumulation layer total capacitance Cacc is a little smaller than the standard value calculated by (4.6). In above discussion, we ignored the surface states of the semiconductor. Figure 4.5 shows an oxide layer–semiconductor interface. There are three main types of states on a surface of HgCdTe: fixed oxide charges, slow-responding surface states, and fast-responding surface states. The number of fixed oxide charges plays an important role determining the flat band voltage of a device. In a typical

Fig. 4.5 HgCdTe surface states

208

4 Two-Dimensional Surface Electron Gas

˚ slow surface state regime, near the interface within a tunnel distance of about 100 A, the minority carrier interface-trap effect causes a shift of the ideal MOS curve along the voltage axis. The fast surface states cause the measured C -V characteristic curve to deviate from the theoretical prediction discussed above and causes an excess dark current. This deviation depends on the frequency of the bias voltage, the temperature, and the surface potential. The generation-recombination mechanism caused by fast interface states and that caused by bulk Shockley-Read centers follow the same dynamics. Figure 4.6 shows an n-type semiconductor in depletion, including the semiconductor surface states. The thermal generate rate Nfs can be modeled as effective resistances Rn;s and Rp;s . These resistances act at the edge of energy band and will vary exponentially with the corresponding energy band in response to the gate potential. Figure 4.6 shows the contribution of the dark current due to the minority carriers. This dark current is generated by the generation-recombination mechanism that produces minority carriers in the neutral body and in the depletion layer. The equivalent circuit displayed in Fig. 4.7a accurately models the behavior of an MIS device in depletion and/or inversion (Lehovec and Slobodskoy 1964). It includes the minority carrier response time in inversion and the surface state effects we discussed above. For the case of strong inversion, Rn;s ! 1, Rp;s ! 0, and .!Cinv /1 D .!Cs /1 , then the circuit in Fig. 4.7a simplifies to that in Fig. 4.7b.

Fig. 4.6 A schematic of an n-type semiconductor in depletion, including its surface states

Fig. 4.7 The equivalent circuit model of an n-type MIS device. (a) in depletion/inversion and (b) in strong inversion

4.1 MIS Structure

209

Analyzing the circuit in Fig. 4.7b results in an expression for the MIS device admittance: Z 1 D

2 j!Œ1 C ! 2 Rd2 Cd .Cox C Cd / ! 2 Rd Cox C D Gm C j!Cm 1 C ! 2 Rd2 .Cox C Cd /2 1 C ! 2 Rd2 .Cox C Cd /2 (4.10)

2 In the low-frequency range, !Rd .Cox C Cd / < 1, (4.10) becomes Gm D ! 2 Cox Rd , Cm D Cox . In the high-frequency range, !Rd .Cox C Cd / > 1, Cm D Cox Cd =.Cox C 2 =.Cox C Cd /2 . Therefore, much information can be gleaned Cd /, and Gm D Rd1 Cox by measuring the C -V curves of an MIS device under strong inversion. For example, we can learn the impurity energy level and the minority carrier-induced dark current. To estimate the fast surface state parameters Cs and Rs , it is necessary to measure the MIS device in the depletion/weak inversion regime and to extract information from the entire equivalent circuit in Fig. 4.7a. The extent of the information obtained from this kind of measurement technology can be found in the reference literature (Nicollian and Goetzberger 1967; Kuhn 1970; Amelio 1972; Tsau et al. 1986).

4.1.2 Quantum Effects In the above analysis, when a positive voltage is applied to an MIS p-type semiconductor structure, the energy bands at semiconductor interface bend downward to form a potential well. Electrons accumulate in this inversion layer formed by the potential well. According to classical theory, electrons continuously gather in this potential well as the positive potential increases and the energy bands bend more. That is in agreement with the test result when the degree of energy band bending is small. For a large energy band bending, we must consider quantum effects. In this situation, the electron energy is not continuous but is quantized at an interface quantum well. Electrons are free to move in the plane parallel to the interface, but have quantized energy levels for the spatial dimension normal to the interface. Quantization into a set of discrete levels is expected that constrains the electron motion in the normal direction. In this potential well, a two-dimension electron gas is formed. A two-dimensional electron gas (2DEG) is a system (Ando et al. 1982) in which electrons have quantized energy levels for one spatial dimension, but are free to move in two spatial dimensions. Since the 1970s, scientists have paid a high degree of attention to 2DEG systems because it not only engenders academic interest but also has attractive application prospects. Theoretical research on 2DEG systems focuses on the many peculiar phenomena (Dornhaus and Nimtz 1983) found there that do not exist in three-dimensional systems. For example, one finds integer and fractional quantum Hall effects, unusual phase change phenomena, and modified forms of superconductivity. Recently, people have found that oxide high-temperature superconductivity is also a two-dimensional phenomenon (Xiong 1987). The twodimensional carriers in a Cu–O interface play a primary role in superconductivity. In an aspect of application research, Kinch (1981) recently developed a

210

4 Two-Dimensional Surface Electron Gas

hetero-junction optical detector. But Hall devices, MIS units, multielement detectors etc. are all based on the special physical properties of two-dimension systems. With the advance of science, two-dimensional systems can be attained easily in the laboratory, such as an electron gas at the liquid helium and vacuum interface, the accumulation layer or inversion layer of metal-insulator-semiconductor structures, and electron and hole gasses at a hetero-junction interface. These systems are all two-dimensional well systems. However, in these systems, their electronic wave functions extend over a limited but finite range along in the quantized spatial dimension (about 10 nm), so we still cannot call these systems ideal two-dimensional systems. Even so, this kind of quasi two-dimensional system still basically reflects the special character of an ideal two-dimensional system. Most of the two-dimensional system photoelectrical research is all based on the quasi two-dimensional system discussed earlier. There are by now many research methods developed to study two-dimensional systems. Theoretical research methods used include the Hartree effective mass approximation and the variational self-consistent method (Dornhaus and Nimtz 1983). Experiment methods used include interband optical transitions, magneto-optical transitions, electrical and magnetic transport, and cyclotron resonance (Dornhaus and Nimtz 1983). The research aim is to clarify the subband structure and properties of 2DEG systems, such as the subband energy dispersion relations, electron effective masses, and electron wave function distributions. So far, many researchers have addressed the physical properties of two-dimensional systems in wide bandgap semiconductor materials, such as Si, and GaAs. Few research projects on narrow gap semiconductor materials (such as MCT and InSb) have been reported. The reason is that the 2DEG narrow-band materials systems are harder to prepare. In recent years, because of the advancement of preparation technology of narrow-band semiconductor MIS devices, the research into the properties of narrow-band semiconductor 2DEG systems has made great progress. Take inversion layer 2DEG of MIS devices as examples. 2DEG systems of narrow bandgap semiconductors (MCT and InSb) have several unique properties compared with those of 2DEGs of wide bandgap semiconductors (Si and GaAs): 1. Electron effective masses are small and state densities are low; there are many subbands filled with electrons in these 2DEG systems. 2. The band edges of both the conduction and valence bands of the narrow gap semiconductors MCT and InSb are located at the point, so the energy-valley degeneracy is 1 (gv D 1) and their subbands in 2DEG are nondegenerate. While the subbands in 2DEG Si are degenerate, so its degeneracy is decided by the crystal orientation. 3. The electron mobility is higher because their effective masses are small, and at low temperatures, the states occupied have long wavelengths, so interface scattering caused by roughness and other imperfections is weaker. In addition, the state density is small and many-body effects can be ignored because correlation and exchange energies are a small part of the subband electron energies. 4. The smaller band gap leads to nonparabolic energy bands, so the quantized part of its subband energy is influenced by the nonquantized part to produce unique properties.

4.2 A Theory That Models Subband Structures

211

5. At a critical applied electrical field for a given band gap, the conduction band and valence band wave functions will overlap, and then the 2DEG subband has completely different properties compared with those of the wide band gap semiconductors. Tunneling effects are examples. This chapter emphasizes the inversion layer-induced 2DEG system in an MIS structure of p-type narrow bandgap semiconductors MCT and InSb. The issues treated include the subband structures, the ground state at the bottom of the subband, the excitation level of this ground state, the wave function distribution, the range of the quasi two-dimensional electron gases distribution, and the thickness of the depletion layer and its variation with the 2DEG electron area density. The special properties and new quantized character of these narrow gap semiconductors are treated in this discussion. In this chapter, we adopt a more convenient capacitance-voltage measurement method, and establish a quasi-quantized theory set based on the experimental technology. This combination provides a new approach to the study of two-dimensional subbands.

4.2 A Theory That Models Subband Structures 4.2.1 Introduction We first discuss a theoretical model of an electron subband structure in an inversion layer. There are several existing theories that have been used to solve the hetero-junction 2DEG system problem. However, because a narrow bandgap semiconductor displays new properties, these theories cannot be taken over to solve the 2DEG system problem of a narrow bandgap semiconductor. This chapter formulates another view of the character of two-dimensional narrow bandgap systems, establishes a series of models to interpret experimental results, and then solves for some related parameters. This section and the next two following sections establish three models that predict experimental results: for a subband model of the ground state of a 2DEG, for a capacitance-voltage model of quantum-limited and nonquantumlimited situations, and for a subband potential model of a 2DEG. Finally, we test these predictions against a series of experimental results on the semiconductors MCT and InSb. The subband electron behavior in the inversion layer of a p-type narrow bandgap MCT semiconductor provides an attractive way to confirm the properties of the subband electron ground-state energy E0 , deduced from studies of the electron Landau energy level and magneto-optic resonance (Chu et al. 1990a). From the quantum capacitance spectrum, the magnetic conductance oscillating spectrum, and the cyclotron resonance spectrum of a p-type MCT MIS structure, we can extract all the properties of the subband structure, including its ground-state energy E0 , its electron effective mass, the thicknesses of the inversion and the depletion layers, the Fermi level and its variation with the concentration of surface electrons. The calculation

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of the ground-state energy has already been developed for both a single band and multibands. It starts from the Poisson and Schr¨odinger equations and employs a self-consistent solution method. However, the calculational process is complex, the result does not agree well with experimental results (Sizmann et al. 1990). In this section, we will develop an improved calculation to one that accurately describes this subband structure. To do this, we add some influential factors, the nonparabolic property, a wave function averaging effect, the resonant defect state of p-type materials, and resonant tunneling of the inverted MIS structure. Then deduce a formula for the subband ground-state energy E0 and its variation with the surface electron concentration that agrees well with experimental data. Subband inversion layer studies of narrow bandgap semiconductor MIS structures have important consequences in the development of infrared detectors. For a p-type Hg1x Cdx Te semiconductor, the Fermi level lies close to the valence band top. When an applied bias voltage inverts the surface, and a quantum well forms to produce a distribution of quantized energy states normal to the surface and a 2DEG subband distribution parallel to the surface, it greatly affects detectors behavior. In an Hg1x Cdx Te semiconductor, inversion layer with subbands forms when the electrical field reaches E  105 V=cm. The ground-state electron energy E0 , for an electron effective mass with an order of magnitude, m  0:01m, and a thickness, z0 , of the inversion layer quantum well, are easily estimated from the uncertainty relation (Koch 1975): p (4.11) p0 z0 D 2m E0  z0  „: For a triangular quantum well approximation: E0  eEz, then 8 .e„E/2=3 ˆ ˆ  100 meV; <E0  .2m /1=3 2=3 „ ˆ ˆ : z0   10 nm .2m eE/1=3

(4.12)

In this triangular approximation, the thicknesses of the well for the higher excitedstate energy levels E1 ; E2 ; : : :, are larger. Their energies can also be estimated from the uncertainty relation. Since the narrow bandgap semiconductors we plan to study have their valence band maximum and conduction band minimum lying at the point, the electron band is highly nonparabolic and has a very low effective mass and therefore a low state density (about 1012 cm2 ), several surface quantum well states are always populated. Furthermore, the conduction band’s strong nonparabolic behavior leads to a very large coupling between the 2DEG’s motion parallel to surface with those in states normal to the surface. These complicate the dispersion relations. Another example is inversion layer electrons penetrate (tunnel) into continuous valence band states and cause a Fano resonance effect. (Fano 1961) Another notable characteristic of a narrow bandgap semiconductor inversion layer electron subband is that the spin degeneracy disappears because of the existence of the surface potential. For a bulk sample, the perturbation .rU  k/   term related to the spin–orbit interaction

4.2 A Theory That Models Subband Structures

213

will lift the heavy hole band’s twofold degeneracy. When a very large electrical field is applied perpendicular to the sample’s surface, the perturbation term has a great influence on the subband structure. This leads to the subband having a larger electrospin-splitting effect. This effect causes the subband’s dispersion relation to split into two branches, even under a zero magnetic field, and leads to a series of new phenomenon: a Landau level shift, and an interface-induced mixing of the Landau level wave functions. In first principle theories that do not include the exchange interaction, all semiconductors have predicted band gaps that are too small (Chen 1993; van Schilfgaarde 2006). Once the exchange interaction that goes beyond the Hartree approximation and other less important corrections are included, the band gaps are correctly predicted. This statement also applies to narrow gap semiconductors. The theories presented here depend on the Kane theory in which the band gap is a parameter that is taken to agree with experiments. Because the exchange interaction is not explicitly included here, there is a chance that it could make a meaningful correction to these results. A narrow bandgap semiconductor electron energy band structure consists of a conduction band (a double degenerate 6 band), two valence bands (quadruple degenerate 8 bands), and a spin–orbit split band (a double degenerate 7 band). The energy separation between the 6 and the 8 bands is very narrow, whereas the 7 lies bellow 6 and 8 bands,   Eg . Near the point, the energy band structure of narrow bandgap semiconductors can be well approximated by the Kane model, as long as the fundamental gap and P matrix elements are set equal to their experimentally observed values. In 1972, Stern (1972) deduced the kind of self-consistent calculational method that is used to deal with the subband structure of silicon a parabolic energy band semiconductor. This theory is one of the foundation methods for narrow bandgap semiconductor surface electron subband structures. However, complexities engendered by, for example, energy band mixing and nonparabolic behaviors cause the calculations to become difficult. Here we just briefly introduce an overview of the problems associated with this research. Ohkawa and Uemura (1974), using a triangular quantum well surface potential, diagonalized the Kane Hamiltonian within the Wentzel-Kramers-Brillouin (WKB) approximation, and then calculated the Hg0:79 Cd0:21 Te subband dispersion relation. They found a large spin-splitting effect in the dispersion relations, as well as an inversion phenomenon in the Landau levels. However, their calculation is not self-consistent, so it is hard to compare it quantitatively with experimental results. Takada et al. (Takada and Uemura 1977, Takada et al. 1980, 1982) have reported a Hartree self-consistent calculation. They developed a method that reduces the 6  6 Kane Hamiltonian matrix into a 2  2 matrix; thereby, simplifying the problem into a one-band approximation. In their calculation, the nonparabolic nature of the conduction band was included through the introduction of a k-dependent electron effective mass, but the interaction between the conduction and valence bands has been ignored. Starting from the 6  6 Kane Hamiltonian matrix, Marques and Sham (1982) calculated the InSb subband structure by a self-consistent calculational method. In principle, this method is also suitable for Hg1x Cdx Te. Zawadzki (1983)

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formulated a k  p theory, deduced subband structures, and developed an optical transition theory of the subband electrons. He adopted the triangular quantum well approximation but did not consider spin splitting terms, so his calculation is based on a 4  4 Hamiltonian matrix. The dispersion relations obtained this way are different from the result based on the more precise 66 matrix. Merkt and Oelting (1987) adopted a three-level version of k  p theory along with a triangular quantum well approximation of the surface space charge layer, in a 6  6 matrix calculation of the subband structure. After this, Malcher and Oelting (1987) also extended this calculation to treat 2  2, 6  6, and 8  8 matrix versions. However, the Zener tunneling effect was not included in all of the above calculations. But, since narrow bandgap semiconductor subband energies can mix the states, this effect is very important. Brenig and Kasai (1984) deal with the Zener tunneling effect by a Green function method, and calculated the width and shift of subbands caused by it. Their theory is based on a theory by Takada (1977, 1980, 1982). During calculations of narrow bandgap semiconductor subbands, the coupling between the valence and conduction bands plays a very important role. There are two coupling mechanisms: one is k  p coupling of bulk band structure; the other is the Zener coupling caused by the surface electric field. The former leads to nonparabolic energy band structures and a two-dimensional subband state density that depends on energy. This can be treated by a suitable kinetic energy operator in the subband calculation. The later leads to a degenerate subband state resonance character and a continuous bulk valence band state, which adds width to the subbands. R¨ossler et al. (R¨ossler et al. 1989; Ziegler and R¨ossler 1988) presented a detailed discussion of this treatment. However, it is not easy to deal with this problem accurately. This leads some researchers (Nachev 1988; Chu et al. 1991b) to study the influence of the k – linear term spin–orbit interaction to the subband structure. This new method and its results are presented in Sect. 4.2.2.

4.2.2 A Self-Consistent Calculational Model First for an ideal situation, one must consider the interband interaction when a model by Stern (1972) is used to deal with MCT inversion layer subband structures. To a certain extent, the interband interaction can be embodied in a subband election effective mass m .E/ related to an energy found from the Kane model (Chu et al. 1991b; Nachev 1988). Figure 4.8 depicts the energy band bending of a p-type MCT MIS structure when it is inverted. E.z/ D eˆ.z/ is the energy at a distance z from the surface, where ˆ.z/ is the potential variation. The ground-state wave function parameter is calculated from the expression j0 D Z0;av =hZi0 [defined in (4.18) and (4.19)], then E  E0 j0 is the average ground-state subband electron energy referenced to the conduction band edge. According to the literature (Chu et al. 1991b) and considering interband interactions, the effective mass of electrons in the inversion layer-induced ground-state subband is given by:

4.2 A Theory That Models Subband Structures

215

Fig. 4.8 Energy band bending diagram of a p-MCT MIS structure when it is inverted

  2.E  E0 j0 / m : m .E/ D 1 C Eg 

(4.13)

Here m0 is electron effective mass at the bottom of the conduction band. In Fig. 4.8, the inversion layer subband system is deduced from the onedimensional Poisson equation and the Schr¨odinger equation. Because the MCT inversion layer subband electron effective mass is small, and the state density is low, we can ignore electron–electron interactions in the subband. Also we suppose that (1) at T D 4:2 K, the system is in a quantum limited state with the Fermi level EF pined at an acceptor level EA , (2) there are no resonant defect states in the material, (3) the MIS structure depletion layer is thick enough so that Zener tunneling cannot occur, and (4) the depletion thickness drops quickly to zero in the transition region. So this subband system can be modeled by the following set of simplified equations: Œdep .z/ C s  d2 ˆz D ; dz2 "s "0 2m .E/ d2 0 .z/ C ŒE0 C eˆ.z/0 .z/ D 0; 2 dz h2 eˆs D .Eg  EA / C EF ; Z EF Z EF  m .E/ Ns D D.E/dE D dE; h2 E0 E0 R1 2 z .z/dz ; hZi0 D R01 20 0 0 .z/dz R hZi0 2 z .z/dz Z0;aV D R0hZi 0 ; 0 2 0 .z/dz 0 and ZR D

.EF  ER / hZi0 : E0

(4.14) (4.15) (4.16) (4.17) (4.18)

(4.19)

(4.20)

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4 Two-Dimensional Surface Electron Gas

Here we have dep .z/ D 0;

.z > Zd /;

dep .z/ D eNAD D e.NA  ND /; .0 < z < Zd /; eNs ; .0 < z < hZi0 /; s .z/ D  hZi0 and EA D 0:0165  2:4  108  NA1=3 . (Scott et al. 1976). In (4.16), the first term on the right is the energy difference between the bulk conduction band edge, Ec , and the Fermi level, EF . We assume that the Fermi level coincides approximately with the acceptor level in the bulk material, and the second term is the energy difference between the conduction band edge and the surface Fermi level. 0 .z/ D .b 3 =2/1=2  z  exp.bz=2/ is the zeroth order FangHoward function (Fang and Howard 1966), and b is a parameter. ‰0 .x; y; z/ D 0 .z/  e i z  e i.kx xCky y/ is the ground-state subband electron wave function, and  z is a parameter related to the wave vectors kx and ky . Take NA D NAD for highly doped samples. The boundary conditions are ‰0 .x; y; z D 0/ D 0;

(4.21a)

‰0 .x; y; z D Zd / D 0:

(4.21b)

and This is a good approximation for a p-type MCT MIS structure, since the bandgap of the ZnS insulator layer is 3.8 eV, which is far great than the MCT bandgap ( 0:1 eV) with a composition x  0:20. Therefore, we can ignore any wave function penetration into the medium. Considering that few electrons fill the subband ground state and counting only the average effect of the wave function, we can substitute the average effective mass ma for m .E/. By using the boundary condition discussed above and solving (4.21a) and (4.21b), we obtain an expression for the subband energy ground state:    h2 b 2 3e 2 11  Ns 2NAD Ndep1 C : (4.22) C E0 D  8ma "s "0 b 16 b At the bottom of the ground-state band, @E0 =@b D 0, from which we can obtain the parameters:

E00

E0 D E00 C ıE0

2=3 p D .3=2/5=3 e 2 h= ma "s "0 ;

.Ndep1 C 55Ns =96/=.Ndep1 C 11Ns =32/1=3

(4.23)

4.2 A Theory That Models Subband Structures

217

ıE0 D .2NA e 2 hZi20 =3"s "0 /.Ndep1 C 11Ns =96/=.Ndep1 C 11Ns =32/ hZi0 D

.Ns C 2NAD  Zd / C Œ.Ns C 2NAD  Zd /2  8  NAD  "S "0 E0 =e1=2 ; 2  NAD (4.24)

and Ndep1 D NAD  Zd D .2  "s "0 NAD ˆS =e/1=2 :

(4.25)

The surface potential ˆs can be solved from (4.16). The Fermi level EF can be obtained from the integral in (4.17):  1=2 .Eg  2jE0 /2 Eg  2jE0 Eg h2 Ns C C E0 .Eg CE0  2jE0 /C EF D  2 4 m0 (4.26) Equations (4.24) and (4.27) are correlated, so E0 .Ns D 0/, E0 .Ns / and EF .Ns / have to be calculated self-consistently. Let’s discuss a practical situation. In above discussion, we considered the influence of a narrow bandgap semiconductor interband interaction on E0 , then introduced the subband effective mass m .E/, and deduced a modified formula for E0 still under ideal conditions. There are many other influential factors that need to consider in practical MIS devices. For example: 1. In depletion, the thickness region has NAD basically constant. But in the transition region between the depleted region and the bulk, the charge density does not drop sharply to zero. Rather it exponentially decays to zero over the range of a shielding length. The influence of charge in the screening length to E0 contributes to the surface energy band bending. The magnitude of this contribution is approximately, eˆ.1/ s D kT (Stern 1972). This influence of the term is small at low temperature. 2. For high doping (NAD  1017 cm3 ), composition x D 0:21, and a p-type MCT sample, there are theories indicating that positive ion vacancies are occupied by oxygen, aluminum, or silicon ions that leads to a series of resonance defect energy level states that lie above the conduction band edge. Recently, experiments have found that there exists an acceptor resonance defect state between the conduction band edge and the subband ground-state E0 . Its distance to the conduction band edge is about 45 meV, and its concentration NR is about 30– 40% NA . In general, it does not bind electrons and is neutral (Chu et al. 1989). In the above ideal situation, consider that the subband ground state is filled with electrons when it is inverted. But in fact, when there is a resonance defect state, electrons also fill these energy levels prior to filling the ground state. So the presence of these resonant states also has an influence on E0 . One part of the effect of the existence of the defects states is equivalent to the thickness of the inversion layer having an additional term, NR ZR , another effect is an additional term 2 2 contributing to the surface band bending, eˆ.2/ s D e NR ZR ="s "0 .

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4 Two-Dimensional Surface Electron Gas

Fig. 4.9 A Zener resonant tunneling diagram for an inverted p-type MCT MIS structure

3. Since the subband energies, En .n D 0; 1; 2; : : :/ of a p-type narrow bandgap MCT semiconductor is close to the bandgap Eg and for highly doped sample, .EF E0 /  EA is easily satisfied, so the subband is located within the continuous valence band. In this case, electrons resonate in the valence band, and will tunnel to degenerated valence band states, leading hopping that broadens the inversion layer subband levels. This is the Zener effect. Brenig et al. (1984) and Zawadzki (1983) have introduced this Zener term and studied its influence on the inversion layer subband levels. R¨ossler et al. (1989) and Dornhaus and Nimtz (1983) have also undertaken a detailed discussion of this effect; however, their calculations are very complex. Here, we will deal with this problem by a simpler method. Figure 4.9 is diagram of Zener resonant tunneling. The probability of electron resonant tunneling from an inversion layer subband level into a degenerate valence state energy E is ) ( Z 2 Z2 Œ2m .U.z/  E/1=2 dz : (4.27) T  exp h Z1 Here we have: Z1 D .hZi0 =E0 /  E Z2 D .hZi0 =E0 /  .E C Eg /: U.z/ D .E0 =hZi0 /  z "

Then we find: Tinv!va1

# .2m /1=2 Eg3=2 hZi0 D exp 4 : 3hE0

(4.28)

From above equations, we see that the tunneling probability depends on only the band gap Eg , the inversion layer thickness hZi0 , the inversion layer subband

4.2 A Theory That Models Subband Structures

219

electron ground-state energy E0 , and the subband electron average effective mass ma . Eg and hZi0 are small, so the Zener tunneling effect is more evident and Tinv!va1 approaches unity. The number of electrons that form the inversion layer and can tunnel into the valence band is: " #   1=2  3=2 Z Ev Eg 9 m T .E/  D.E/dE  Ns exp 6:58  10 hZi0 : NST D m0 E0 E0 (4.29) In this equation, the energy units are electron volts and the thickness units are meters. The influence of electrons tunneling on E0 has two aspects: one aspect is its contribution to the total electron density in the inversion layer NST ; the other is its 2 contribution to the surface energy band bending, eˆ.3/ s D e NST hZi0 ="s "0 . Consider the above factors, ˆs and Ns in (4.24–4.26) can be amended to ˆs , and  NS , and Ns in (4.27) can be amended to Ns  NST . Then we find: .2/ .3/ ˆs D ˆs C ˆ.1/ s C ˆs C ˆs ;

(4.30)

Ns D Ns C NR ZR  NST :

(4.31)

Substitute the above additional factors into (4.31). Then we find:  eˆs D Eg  EA C EF  kT 

e 2 NR ZR2 "s "0

C

e 2 NST hZi0 "s "0



;

(4.32)

Ndep1 D 1:110  104 Œ"s NAD ˆs 1=2 ;

(4.33)

E0 D E00 C ıE0 :

(4.34)

Here we have defined new variables: 3=2

E00 5:6  1012 .ma =m0 /1=3 "s

ıE0 1:2  108

.Ndep1 C 55Ns =96/  .Ndep1 C 11Ns =32/1=3

NAD hZi20 .Ndep1 C 11Ns =96/ .Ndep1 C 11Ns =32/"s

In these equations, the energy units are electron volts, the length units are meters, and the area units are meters squared. Equations (4.33–4.35) are interrelated, so the inversion layer structure parameter must be obtained from a self-consistent calculation. The calculational results will be discussed in the following paragraphs. The MCT inversion layer subband structure parameters can be obtained from (4.33–4.35), These include the ground-state subband energy E0 , the inversion layer and depletion layer thicknesses, the Fermi level, and their variation with the surface electron concentration Ns . From (4.18) and (4.19), we can also find the distribution parameter for the ground-state wave function: j0 D 0:162. Figure 4.10 is a calculated result for an x D 0:21 sample’s variation of E0 and EF with Ns . Experimental points and related parameters come from the literature

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Fig. 4.10 The variation of an x D 0:21 sample’s (NAD D 1:87  1017 cm3 / variation of E0 and EF with Ns

Table 4.1 The calculational result for E0 and EF in different approximations

T D0 RD0 T D1 RD0 T D0 RD1 T D1 RD1

NS .cm2 / 0 8  1011 0 8  1011 0 8  1011 0 8  1011

E0 .meV/ 114.02 186.03 114.05 178.87 117.20 190.96 117.24 184.35

EF .meV/ 114.00 273.90 114.00 267.66 117.00 277.91 117.00 272.00

(Chu et al. 1989): with data taken at T D 4:2 K, and parameters: "s D 17, NAD D 1:87  1017 cm3 , NR D 9  1016 cm3 , and ER D 45 meV. Electrons fill the levels between E0 and EF when the surface inversion layer electron concentration is Ns . Considering the electrons to be in a Fermi-Dirac distribution and the wave function averaging effect, we deduce an effective mass that differs from that at the conduction band edge, .EF E0 /=4C.E0 E0  j /, as the electron average effective mass in our calculation. Solid curves are calculated results including tunneling effects, and the round spot are experimental data. In order to compare the results quantitatively, Table 4.1 show the influence of the resonant defect state and tunneling effect on E0 and EF when they exist separately, R D 0 denotes no resonant defect state, R D 1 denotes that there are resonance states, T D 0 denotes no tunneling effect, and T D 1 denotes that there is a tunneling effect. From the table, it is obvious that the calculated results for E0  Ns and EF  Ns curves will be on the low side if one does not include resonance defect states, and will be on the high side if one does not include the tunneling effect. The larger the inversion layer electron concentration, the larger the influence of the two effects. These conclusions agree with those of Sizmann et al. (1990). So the influence of the two effects must be considered in any practical calculation. We also calculated for an x D 0:21 sample, the variation of E0 with the bulk doping concentration in two situations (Dornhaus and Nimtz 1983). Ns  81011 cm2

4.2 A Theory That Models Subband Structures

221

Fig. 4.11 The variation of E0 with the bulk doping concentration when Ns  8  1011 cm2 and x D 0:21. The dots are experimental data and the solid curve is from theory calculation

Fig. 4.12 The variation of E0 with the bulk doping concentration when Ns  0 cm2 and x D 0:21. The triangles are experimental data and the solid and dashed curves are from theory calculation

(Fig. 4.11), the solid curve includes the Zener effect, and the dashed curve does not (Chu and Mi 1987). Next we take Ns  0 (Fig. 4.11), where the tunneling effect is not included, though in this case, the doping concentration may be very high. However, few electrons tunnel to the valence band so the contribution to the band bending effect can be ignored. The parameters entering the calculation come from literature (Chu et al. 1989; Chu and Mi 1987; Chu 1985a): T D 4:2 K, NR D 35%NA , ER D 45 meV, and "s D 17. The triangles in Fig. 4.12 are experimental results from the literature (Sizmann et al. 1990). In Fig. 4.11, the influence of tunneling on E0 causing it to increase with an increase of the doping concentration is shown. This is caused by a thinning of the inversion layer with an increase of the doping concentration that leads to the material entering into a strongly degenerate state. Then the ground-state energy E0 lies below the valence band edge and enhances the tunneling effect. In Fig. 4.12, the calculated result (solid curve) is more consistent with the experimental data than is a multiband model (Chu and Mi 1991) (dashed curve). One of the reasons for this deviation between multiband model and experiment is that this model does not account for the Zener effect. R. Sizmann thinks that E0 will decrease when this effect is included (Sizmann et al. 1990). The other main reason for the multiband model’s deviation probably is that it does not treat the averaging effects on the subband wave function or the subband electron effective mass.

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As can be seen from above discussion, according to the Stern model, the introduction of a wave function distribution parameter, the subband electron average effective mass, considering the Zener tunneling effect, resonance defect states, and carrier decay within a shielding length, as influential factors, lead to a self-consistent calculational formula for the subband structure. The results calculated from this formula agree well with a p-type material’s experimental results. This theory indicates that the presence of resonant defect states leads to a subband ground-state energy that increases, whereas the Zener effect leads to a subband ground-state energy that decreases; the net effect is augmented by an increase of the inversion layer electron concentration and the doping concentration.

4.3 Experimental Research on Subband Structures 4.3.1 Quantum Capacitance Subband Structure Spectrum Model Since the charge density derived from the Poisson equation is coupled to the subband electron wave function distribution obtained by solving the Schr¨odinger equation and the surface potential function in the Schr¨odinger equation enters into the Poisson equation, a self-consistent theory is used to solve both equations. It begins by substituting .1=i /@z for kz in the Hamiltonian for the subband and adding the surface potential:   1 Hsubband D H88 kz ! @z C V .z/I88 : i

(4.35)

However, the usual self-consistent calculation depends on the selection of boundary conditions, so it does not always agree with the experimental results. For example, subband energy levels calculated for boundary conditions in which the wave functions exponential decay differ by 10–20 meV with results calculated for boundary conditions where the wave functions are taken to be zero in the middle of the band (Malcher et al. 1987). So we must not only improve the theory of subband energies but also establish a method that can directly obtain important properties from subband experimental data. That is, we must establish a phenomenological theory of the subband structure that can output subband structures from inputs derived from experimentally measured results. The result obtained from this method is subject to further testing by comparing its predictions against other experiments, for example, magneto-optical resonance phenomenon, Zener resonance, spin–orbit interactions, and contributions from k and k 3 terms. It also used to allow comparisons between different theory models. This section chiefly discusses an n-type inversion layer subband behavior as a consequence of an inversion layer forming in a p-type Hg1x Cdx Te MIS structure within the electrical quantum limit condition. A focus is on the occupation of the ground-state subband, and once that is settled various physical properties

4.3 Experimental Research on Subband Structures

223

Fig. 4.13 The surface energy band bending diagram in the inversion layer of a p-type Hg1x Cdx Te MIS structured sample

of the subband can be displayed more clearly. Figure 4.13 shows the surface energy band bending diagram of the inversion layer of a p-type Hg1x Cdx Te MIS structured sample. In Fig. 4.13, V .z/ D .z/ is the negative value of the surface potential, E0 is the subband ground-state energy level at zi , EF is the Fermi energy level, D.E/ is the subband electron state density, zi is the thickness of the inversion layer, zd is the thickness of the depletion layer, zav is the average distance between an electron inside inversion layer and the surface, and E0;av is the average value of the subband electron ground-state energy level inside inversion layer relative to the conduction band edge. In order to approximately solve the Schr¨odinger equation, we assume that the subband energy E0 formula can be developed in terms of a series expansion of the surface electron concentration Ns , and then introduce a first-order term E01 , a second-order term E02 , and a characteristic parameter j zav =zi used to describe the wave function distribution (that is we approximate the subband electron to be distributed mainly in thickness zavt /. Adopting these simplified energy and wave function expressions, we solve the Schr¨odinger and Poisson equations to obtain the subband structure. In order to establish the physical parameters introduced in this theory, we need to fit measured C -V curves and an experimental value of the effective mass obtained from a cyclotron resonance experiment Also we need to fit the relation between Ns and the bias voltage obtained from a surface magnetic conductance (SdH: Shubnikov-de Haas)) oscillation experiment. Through these fittings, we can deduce a set of detailed quantitative properties of a subband structure as functions of Ns . According to this physical idea, we can write the follow equation set (Chu et al. 1990b, 1991a): 8 2 d  .z/ ˆ ˆ D ˆ ˆ 2 ˆ dz ""0 ˆ ˆ ˆ ˆ E D E C E01 Ns C E02 Ns2 0 00 ˆ ˆ < zav E0  E0;av ; (4.36a) j D D ˆ ˆ zi E0 ˆ ˆ ˆ R EF m .E/ ˆ ˆ N D dE ˆ s E0 ˆ ˆ „2 ˆ : es D EF C .Eg  EA /

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where .z/ D s .z/ C dep .z/  eNA ; .0 < z < zd / dep .z/ D : 0.zd 6 z/ X 2 Ni i .z/ s .z/ D e

(4.36b)

i

The expression for E0 and j substituted into the Schr¨odinger equation to a certain extent will be confirmed by fitting experimental results to E01 and E02 and finding that they are small. Analysis indicates that E0 expanded to quadratic terms in Ns are sufficient to describe the relation between the subband energy E0 and Ns in the range of Ns 6 8  1011 cm2 . The value of Ns can be deduced from expressions in the literature (Ando et al. 1982) and considering that there is a nonparabolic band. .z/ is an envelope function of the subband electron wave function and takes on the common form of a Fang-Howard wave function (Fang and Howard 1966):  0 .z/ D

1 3 b 2

1=2

ze bz=2 :

(4.37)

In this wave function expression(4.39), the parameter b and the wave function distribution parameter j are interrelated, and j can be obtained by fitting experimental results. If the area of an MIS structure is A, then according to (4.36), we have the expressions:   @zd @Ns  A; C NA Cs D e @s @s C D

Ci C s C i C Cs

where

Ci .Vg  Vt /  NA zd ; eA

(4.39)

m .E/ 2.E  jE0 / D1C ;  m0 Eg

(4.40)

NS D and

(4.38)

enabling us to calculate the capacitance spectrum, effective mass, and the relation between Ns and Vg . By fitting the experimental results to these parameters, we can determine the physical parameters related to E0 and j , and from them determine the subband structure. After we determine the effective mass, it allows us to specify the wave function. If we assume that the electrons are located at the average location in the plane separated at displacement zav , from the surface, then the energy difference between the electron energy in this plane and the conduction band edge is Eav D E  jE0 :

(4.41)

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225

The formula for the subband electron effective mass is given by (4.42). In above expression, the calculated expression from (4.40) is fitted to the C -V experimental result. The calculated result from (4.41) must agree with the relation between Ns and Vg obtained from the SdH experiment, and the calculated result from (4.42) must coincide with the effective mass deduced from the cyclotron resonance experiment. In (4.36), E00 is given by: E00 D

Ci2 .Vt  VFb /2  .Eg  EA /: 2""0 eNA A

(4.42)

Here Vt is the threshold voltage for the onset of inversion. Since the smooth part of a C -V curve in the depletion region goes through the .VFb , Ci / point, one of the parameters VFb or Ci is an undetermined coefficient. In the fitting procedure, j , E01 .E02 /, and VFb are regarded as three adjustable parameters. The calculated result must agree with cyclotron resonance, SdH, and C -V curve fits, so it is unique. In this way, physical quantities related to Ns and the subband structure can be obtained. The detailed calculational process can be found in the reference (Chu et al. 1991b). In order to implement the above model to get a subband structure, we need to measure a sample’s C -V , SdH, and cyclotron resonance spectra. Experimental samples are selected to be MIS structures of p-type Hg1x Cdx Te. After polishing and etching a p-type Hg1x Cdx Te sample, we grow either a layer of anodic oxide film on it to a thickness of about 90 nm, or a 1-m-thick film of ZnS is evaporated onto the substrate. Then about a 1 m thick layer of lacquer us coated onto either type of the underlying passivation layers, and finally a last evaporate metal grid electrode is applied. Thus, there are two kinds of insulation layers on samples: (1) ZnS C lacquer and (2) SiO2 C lacquer. We measure the C -V curve by a differential capacitance method to a precision of 0.005 pF/V (Chu et al. 1991b). To measure the surface conduction, magnetic field-induced oscillating conductance, and the cyclotron resonance of samples, a thin semitransparent Ni-Cr alloy metal grid electrode is evaporated on the surface followed by concentric circle of aluminum electrodes. A high-frequency voltage of about 102 MHz is applied between concentric ring electrodes. This results in a high-frequency current across the sample’s surface. Simultaneously, a low-frequency bias voltage is added, then surface conduction is measured by a lock-in-phase sensitive technique. If a longitudinal magnetic field is applied normal to the surface, then the SdH effect can be measured. Figure 4.14 shows the C -V curve, the surface conduction, and the SdH effect curve at B D 7 T. If one adds a farinfrared laser applied normal to sample’s surface and parallel to a scanned magnetic field, then by measuring the flat band voltage VFb and reflection index difference R with and without a bias voltage Vg , a cyclotron resonance signal can be measured. Figure 4.15 displays the surface cyclotron resonance curves for x D 0:234 p-type Hg1x Cdx Te samples prepared by liquid phase epitaxy (LPE) with different surface electron concentrations. From this figure, we see a cyclotron resonance peak and its movement with Ns . The effective mass of the subband electrons at the Fermi level can be calculated from the resonant peak’s position.

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4 Two-Dimensional Surface Electron Gas

Fig. 4.14 The inversion layer’s capacitance spectrum, the surface conduction, and the SdH effect curves at B D 7 T of a p-type Hg1x Cdx Te .x D 0:234; NA D 4:0  1017 cm3 / sample

Fig. 4.15 The cyclotron resonance spectrum of a p-type Hg1x Cdx Te .x D 0:234; NA D 4:0  1017 cm3 / sample at different surface electron concentrations NS

For x D 0:234, NA D 4:0  1017 cm3 Hg1x Cdx Te MIS structured sample grown by LPE. The C -V curve fitted to a calculated expression is denoted by the dashed line in Fig. 4.14. Table 4.2 contains the fitted parameters and related physical quantities. In Fig. 4.16, “o” denotes the Ns -Vg relation obtained from the C -V fit, and “” denotes that obtained from the SdH oscillation experimental data. In Fig. 4.17, the solid curves show the m .E/  Ns relation obtained from the C -V fit, and “” denotes cyclotron resonance experimental data. From Figs. 4.14, 4.16, and 4.17, the fitted curves deduced from the above model agree with the experimental C -V , SdH, and cyclotron resonance results. Then a sample’s subband structure can be gleaned that agrees with an actual situation. The surface energy band bending and the subband structure when the surface electron concentration is Ns D 3  1011 cm2 are shown quantitatively in Fig. 4.13. Figure 4.16 shows the variation of the subband ground-state energy level E0 and

4.3 Experimental Research on Subband Structures Table 4.2 Ci (pF) 54.65

Some relevant physical parameters for a liquid phase epitaxy sample VFb Vi j E00 E01 E02 (V) (V) (eV) (eV) (eV) (eV) 75 0 0.84 0.146 1:2  1012 5  1026

227

Eg (eV) 0.128

EA 0

Fig. 4.16 The variation of a p-type Hg1x Cdx Te .x D 0:234. NA D 4:0 1017 cm3 / sample’s surface electron concentration NS with bias voltage Vg (the “o” are C -V fitted to calculational results and the “” are SdH experimental results)

Fig. 4.17 The variation of a p-type Hg1x Cdx Te .x D 0:234; NA D 4:0  1017 cm3 / sample’s subband electron effective mass with the surface electron concentration NS (“” are SdH experimental results)

the Fermi energy level EF with Ns . In Fig. 4.17, the curves are the variation of inversion layer average thickness z0 and the depletion layer thickness zd with Ns . From Figs. 4.18 and 4.19, we see that when the surface electron concentration Ns increases from 0 to 7  1011 cm2 , E0 from 0.146 to 0.206 eV, the Fermi level EF from 0.146 to 0.276 eV, the depletion layer thickness from 36.6 to 41 nm, whereas the inversion layer thickness variation is small.

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4 Two-Dimensional Surface Electron Gas

Fig. 4.18 The variation of a p-type Hg1x CdxTe .x D 0:234; NA D 4:0  1017 cm3 / sample’s subband ground-state energy level E0 , and Fermi level EF with the inversion layer electron concentration NS

Fig. 4.19 The variation of a p-type Hg1x CdxTe .x D 0:234; NA D 4:0  1017 cm3 / sample’s inversion layer average thickness zi and depletion layer thickness zd with the surface electron concentration NS

We have adopted a physical parameter fitting model, and from the experimental measurements, it directly gives the subband structure’s dependence on Ns . During the analysis, it specially calls attention to the influence of the resonant defect state on the subband structure. For a sample with a high p-type doping concentration of the Hg1x Cdx Te bulk material MIS structure, a peak has been observed in the C -V curve (Chu et al. 1989, 1992) that occurs before the inversion region is reached, which indicates that there is a resonant defect state that lies above the conduction band edge. The electron concentration dependence of this resonant defect state’s peak energy level position and its line shape allow us to calculate its energy. Since an electron bound into a resonant defect state is localized, its fill and release process contributes to the differential capacitance (but not to the cyclotron resonance and SdH magnetic conductance oscillations). Therefore, its contribution must be considered when the C -V curve is fitted. Only then is the correct variation of the subband structure with the surface electron concentration Ns obtained.

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229

4.3.2 Quantum Capacitance Spectrum in a Nonquantum Limit In the inversion layer quantum limit, only the ground-state subband is filled with electrons. In this case, the variation of ground state’s energy band with the electron concentration can be expressed by a second order function in Ns (Chu et al. 1990b, 1991b): (4.43) E0 D E00 C E01 Ns C E02 Ns2 : Here, E00 is the ground-state subband threshold energy, and E01 and E02 are ground-state subband energy parameters. According to semiconductor surface capacitance properties, it is easy to get the contribution of a p-type semiconductor surface 2DEG system to its MIS capacitance (Chu et al. 1990b):  Cinv D e

@Zd @Ns C NAD @ˆs @ˆs

 :

(4.44)

Here, E00 , @Ns =@ˆs and @Zd =@ˆs are deduced from (4.16), (4.18–4.21), and (4.23): @Zd D .2NAD Zd C Ns /1 @ˆs



2"0 "s @.Zd  hZi0 / @Ns CNs  hZi0 e @ˆs @ˆs

@.Zd  hZi0 / .1  @E=@Ns  @Ns =@ˆs / ; D "0 "s @ˆs eNAD .Zd  hZi0 / @Ns =@ˆs D

Œh2 =m0

 : (4.45)

(4.46)

eŒ1 C 2.EF  j0 E0 /=Eg  ; C .E01 C 2E02 Ns /.1 C 2.E0  2j0 E0  j0 EF /=Eg / (4.47)

and E00 D

Ci2 .Vt

2

 VFB / : 2"s "0 NAD  .Eg  EA /

(4.48)

The capacitance of an MIS device in depletion can be calculated from the following equation (Chu et al. 1990b): Cdep1 D

"0 "S e : ŒCi  .Vg  VFB /

(4.49)

Cs is the semiconductor surface capacitance, representing Cinv and Cdep1 separately for different gate voltages. Then the subband structure in the quantum limit can be obtained by fitting to experimental C -V spectra. There are four adjustable parameters to be fit: the inversion layer ground-state subband energy parameters E01 and E02 , the flat band voltage VFB (or the insulating layer capacitance Ci ), and the ground-state electron wave function distribution parameter j0 .

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4 Two-Dimensional Surface Electron Gas

Fig. 4.20 The energy band bending diagram of an MIS structure in the nonquantum limit

In the nonquantum limit, there are at least two or even more than two subbands that are occupied by electrons. Figure 4.20 shows the energy band bending diagram for such a case, Ei (i D 0; 1; 2; : : :) are the i th subband energies, hZii and i .z/ are the penetration depths and wave functions of the i th subband, respectively. Considering interband interactions, the effective mass of each subband is:   2.E  ji  Ei / 0:05966  Eg  .Eg C 1/  m0 :  mi .E/ D 1 C (4.50) Eg Eg C 0:667 ji is the i th subband wave function distribution parameter, and E  E0  ji is the average energy of the i th subband referenced to conduction band edge. ji is solved from the follow equations: hZii;av ; hZii R1 2 z .z/dz hZii D R01 2i ; 0 i .z/dz ji D

R hZii

hZii;av D R0hZi i 0

zi2 .z/dz i2 .z/dz

(4.51a)

(4.51b)

:

(4.51c)

The density of electrons, Nai , in each subband and the sum of the total electron density Ns in the inversion layer are obtained from the following equations: Z

EF

Nsi D Ei

Ns D

X

mi .E/ dE; h2

Nsi :

(4.52) (4.53)

The subband electron effective mass in the inversion layer of MCT is small, and the state density is low, so the interactions within and among the subbands can be ignored. Thus, one can speculate that Ei can be expressed as a series expansion in the

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231

inversion layer electron concentration Ns , and that the quadratic term is sufficient to accurately represent the variation of each subband energy with Ns : Ei D Ei0 C Ei1  Ns C Ei2  Ns2 :

(4.54)

Here, Ei0 is the i th subband threshold energy, and Ei1 and Ei2 are the i th subband energy parameters. In principle, the inversion layer subband system in Fig. 4.20 also can be solved from the coupled one-dimensional Poisson equation and Schr¨odinger equation. Following the same procedure as outlined in Sect. 4.2, the subband structure of a 2DEG system can still be solved through fitting theoretical expressions to an MIS device’s capacitance spectrum. The contribution of a 2DEG system to a MIS device capacitance can still be written as (4.46), where Ei0 , @Ns =@ˆs and @Zd =@ˆs can also be deduced in combination with (4.16), (4.18–4.21), and (4.49–4.54). In the following discussion as an example, examine a situation in which only two subbands are filled with electrons, and deduce concrete expressions to compare with experiments. The Fermi level can be solved from (4.56) and (4.57) when the total electron density in the inversion layer is Ns , and it is  EF D

.Eg  j0  E0  j1  E1 /2 C E0 .Eg C E0  2j0  E0 / 4 1=2 Eg h2 Ns E g  j 0  E 0  j1  E 1 CE1 .Eg C E1  2j1  E1 / C :   .2  mb / 2 (4.55)

For an MIS device, the measured capacitance Cm is the series combination of insulating layer capacitance Ci and semiconductor surface capacitance Cs , namely Cm D Ci  Cs =.Ci C Cs /. Here semiconductor surface capacitance Cs is Cdep1 in depletion calculated from (4.51), and Cs is Cinv in inversion calculated from (4.46), namely Cs D e .@Ns =@ˆs CNAD @Zd =@ˆs /. Here, @Ns =@ˆs D e=.@EF =@Ns / is solved from (4.18) and (4.58), whereas @Zd =@ˆs is deduced from (4.16) and (4.18– 4.21), the detailed deduction process follows. When the electron’s area density in the inversion layer is Ns , the average electron energy Eav of two subbands and the surface potential are ˆs D e  and Eav

.NAD  Zd2 C Ns  Zav / ; .2"a  "0 /

  .2Zd  Zav / C Ns  Zav / : D e  NAD  .2"a  "0 / 2

(4.56)

(4.57)

In these equations, Zav is the average inversion layer thickness. According to Fig. 4.20, an approximate solution for Eav is: Eav D

.Nso  E0 C Ns1  E1 / : Ns

(4.58)

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4 Two-Dimensional Surface Electron Gas

Therefore, @Zd =@ˆs solved from (4.56–4.58) is: @Zd Œ1:105  106 "s C Ns  @.Zd  Zav /=@ˆs  Zav  @Ns =@ˆs  D @ˆs .2NAD  Zd C Ns /

(4.59)

In this equation, we have: 

   @Eav @Ns 1  @.Zd  Zav / @Ns @ˆs D 5:5  106  "s  : @ˆs NAD  .Zd  Zav /

(4.60)

@Eav Eav .E0  @Na0 =@Ns C Ns0  @E0 =@Ns C E1  @Ns1 =@Ns C Ns1  @E1 =@Ns / D C @Ns Ns Ns (4.61)

@Ns1 @Nso D1 ; @Ns @Ns @Ns1 D @Ns



@Ns1 @ˆs

   @ˆs  ; @Ns

@Ns1 .@ˆs =@EF / : D @ˆs e

(4.62)

(4.63)

(4.64)

@Ns1 =@ˆs solved from (4.56), (4.57), and (4.59) is:

@Ns1 D k 0  .2EF C Eg  2j1  E1 / C .4j1  E1  2j1 / @ˆs     @Ns @E1  ;  .E F  2E1  Eg /  @Ns @ˆs with k 0 D 4:16667  1014 

.m0 =m0 / : Eg

(4.65)

(4.66)

Then @Zd =@ˆs can be written as a function that includes @E0 =@Ns , @E1 =@Ns . and @Ns =@ˆs , and be calculated from (4.58) and (4.59). Zav and @Zd are solved from (4.60) and (4.61). Therefore, the depletion region capacitance can be fitted by (4.51). The capacitance spectrum with only one subband filled is fitted by the quantumlimited experimental model (Xiong 1987); whereas when the second subband begins to fill, the nonquantum limit experimental model comes into play, which includes E0 ; E1 ; EF ; Zav ; @Zd , and their variation with the electron concentration in the inversion layer Ns . The fitting process of the two subband contribution to the inversion layer capacitance starts, given the initial values of the parameters Ei0 ; Ei1 , and Ei2 , at a certain bias voltage V , evaluate N s from the C -V spectrum, then calculate E0 ; E1 , and EF ; next calculate @Ns =@ˆs ; @Ns1 =@ˆs , @Ns0 =@ˆs ; @E0 =@Ns ; @E1 =@Ns ; @Eav1 =@Ns ,

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233

and @Zd =@ˆs ; and finally, the capacitance is found from (4.46). When adjusting parameters, E1 is located at the second subband threshold voltage Vt1 and is required to equal EF since electrons are just filling the third subband at this voltage. When the inversion layer has three or more subbands that are filled with electrons, by extrapolating this model one level at a time in the measured C -V spectrum, the multisubband system can be solved.

4.3.3 Experimental Research of Two-Dimensional Gases on the HgCdTe Surface Samples of p-type MCT (x D 0:24) bulk materials were fabricated. They were ground, polished, and etched, and then had been evaporated layers of ZnS insulating layers of about 200 nm thickness deposited on the surface. Then through photolithography, these samples had been evaporated gold layers covering their surfaces, and had been made into MIS devices. The electrode areas were 4:91  104 cm2 . The devices were fixed onto a sample holder with conductive silver glue. A gold thread was used as the lead wire to make the electrode into a good ohmic back contact. A fabricated device is placed into a Dewar and its C -V spectrum is measured using a differential capacitance measurement device at 77 K. The AC frequency is 68.8 kHz and its amplitude is 10 mV (satisfying the small signal requirement). The scanning speed of the DC bias voltage is 120 mV/s. The measured result is a lowfrequency spectrum (the solid curve in Fig. 4.21). From this capacitance spectrum, we see that the saturation speed of the capacitance is low in the inversion layer, which is the expected C -V property of a narrow bandgap semiconductor MIS device. The quantum limit C -V experimental model is adopted to fit this experimental result (the dashed curve). The fitting parameters

Fig. 4.21 The low-frequency capacitance spectrum of a p-type MCT.x D 0:24/ sample in an MIS structure

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4 Two-Dimensional Surface Electron Gas

are Ci D 8:66 pF; Vto D 3:05 V; Nad D 3  1016 cm3 ; j D 0:612; E00 D 68:04 meV; E01 D 1:6  1013 eV  cm2 , and E02 D 8:6  1026 eV  cm4 . From this fit, we obtain the subband structure parameters for the inversion layer, including the Fermi level EF , the electronic ground-state energy E0 , the effective masses m .E0 /=m0 and m .EF /=m0 , the depletion layer thickness Zd , the inversion layer’s thickness hZi0 , and the variation of these parameters with the electron concentration in the inversion layer Ns . This variation is showed as solid curves in Figs. 4.22–4.25. From Fig. 4.22, we see that the surface does not begin to invert and be filled with electrons until the energy band bending quantity gets to E00 D 68:04 meV. When the electron concentration in the inversion layer NS increases from 0 to 2  1011 cm2 ; E0 and EF increase from 88 to 87.40 and 121.70 meV, respectively. The effective masses at E0 and EF increase from 0.0186 to 0.020 and 0:024 m0 , respectively (Fig. 4.23). The depletion layer thickness increases from 107.85 to 122.4 nm (Fig. 4.24), whereas the inversion layer thickness decreases from 20.1 to 19.27 nm (Fig. 4.25) and remains almost constant. Since the sample’s doping concentration is low, the depletion layer thickness is much larger than the inversion layer thickness. Dashed lines in the above figures are calculated results from a selfconsistent variational theory. We see that they agree well with the experimental results.

Fig. 4.22 The variation of ground-state energy level and the Fermi energy level in the inversion layer with the electron surface density

Fig. 4.23 The variation of the electron effective masses of the ground-state energy level and at the Fermi energy level in inversion layer with the electron surface density

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235

Fig. 4.24 The variation of the depletion layer thickness with the electron surface density in the inversion layer

Fig. 4.25 The variation of inversion layer thickness with the electron surface density in the inversion layer

Figure 4.26 shows the C -V spectrum when the bias voltage is scanned forward and then reversed. The capacitance has a 0.3 V hysteresis along the voltage axes, and has no shift along the capacitance axes. A voltage hysteresis effect is caused by the response of slow interface states that are far from the ZnS–MCT interface. Ignoring the influence of other mechanisms, the slow interface state density in this device is estimated to be about 2:1  1010 cm2 . The experimental value of the flat band voltage is 1:45 V that is obtained as a straight line extrapolation from the smooth part of the depletion region capacitance to the voltage p axis. The voltage obtained from the flat band capacitance theory is 1:6 V (CFB D 2  "0  "s =LD /. The difference indicates that there exists some positive fixed charge in the insulator layer, and its density is 1:24  1011 cm2 . It is obvious that the slowly responding interface state and fixed charge densities are both small. The bulk material’s doping concentration NAD obtained from a Hall measurement is 4:5  1016 cm3 . NAD is 3  1016 cm3 obtained from the capacitance spectrum, which is obviously less than the Hall result. The same result is also found in other p-type MCT MIS devices. Since the C -V measurements are sensitive to the doping concentration in a thin layer surface (a few hundred nanometer thick), surface inversion and interface states both influence the doping concentration

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4 Two-Dimensional Surface Electron Gas

Fig. 4.26 The C -V spectrum when bias voltage scans forward and then is reversed (solid curve, forward scan; dashed curve, reverse scan)

Fig. 4.27 The C -V spectrum of a p-type MCT .x D 0:213; T D 4:2 K/ MIS device (solid curve: experimental measurements .f D 238 Hz/; dashed curve: results fitted to the model)

measurements. The former mechanism leads to a result that is too small, and the latter leads to a result that is too large. Measurement results indicate that surface inversion cannot be ignored in MCT. Sometimes it will substantially modify the interface state properties and seriously degrade device performance, which is confirmed by thin film Hall measurements (Huang et al. 1993). The capacitance spectrum in the nonquantum limit can also be observed in experiments. Figure 4.27 shows a low-frequency capacitance spectrum at 4.2 K of an x D 0:213 MCT MIS device whose electrode area is A D 0:176 cm2 and its doping concentration is NAD D 5:8  1016 cm3 . From this figure, we see that the capacitance has two jumps in the inversion region; the first jump at the threshold voltage Vt0 indicates that in the inversion layer, the first subband begin to be filled with electrons, whereas the second jump at threshold voltage Vt1 then indicates that the second subband begins to be filled with electrons. The two threshold voltages read from this experiment are Vt0 D 90:2 V and Vt1 D 25:5 V, respectively. The quantum- and nonquantum-limited capacitance spectrum model fit is shown as the dashed curve in Fig. 4.27. The fitting parameters are "s D 16:5; Ci D 39:528 pF; Vfb D 120:2 VI j0 D 0:8; j1 D 0:7I E00 D 0:0787 eV; E01 D 1:1  1013 eV  cm; E02 D 1:1  1026 eV  cm2 ; E10 D 0:172 eV;

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237

Fig. 4.28 E0 , E1 , and EF verses Ns .Vg /

Fig. 4.29 Zd , and Zav verses Ns

E11 D 1:1  1013 eV  cm, and E12 D 1:0  1026 eV  cm2 . Also by fitting, we can obtained the inversion layer electron concentration variation of the ground-state subband energy level E0 , the first excited-state subband energy level E1 , the Fermi energy level, the depletion layer thickness, and the inversion layer average thickness shown in Figs. 4.28 and 4.29.

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4 Two-Dimensional Surface Electron Gas

Figure 4.28 shows the variation of the subband energy levels (E0 and E1 ) and the Fermi energy level .EF / with the inversion layer electron concentration and the bias voltage. The solid curves are the E0 and EF results calculated from the self-consistent theory model in the quantum limit, whereas the dashed curves are experimental results for E0 , E1 , and EF obtained from fitting the capacitance spectrum. From this figure, we see that the first subband begins to fill with electrons when the bias voltage is 90:2 V, the second subband begin to fill with electrons when bias voltage increases to 25:5 V. Then the electron concentration in the inversion layer is about 9  1011 cm2 . The E0 and EF theory and experimental results coincide before the second subband begins to fill, especially when the electron concentration in the inversion layer is low. While when inversion layer electron concentration increases, the agreement degrades because the self-consistent model holds only if the electron concentration in the inversion layer is low. For this measured MIS device, when the electron concentration in inversion layer increases from 0 to 1:58  1012 cm2 , the first subband and second subband minimum energies increase from 80.14 and 172 to 223.38 and 318.36 meV, respectively, whereas EF increases from 80.14 to 344.71 meV. From Fig. 4.29, we see that when the electron concentration in the inversion layer increases from 0 to 1:58  1012 cm2 , the depletion layer thickness increases from 72.4 to 116.14 nm, whereas the inversion layer average thickness decreases from 20.44 to 16.38 nm. We note that when the second subband begins to fill, the inversion layer average thickness first has only a feeble increase, then decreases with a continuing increase of the electron concentration. This occurs because the second subband begins to fill with electrons.

4.3.4 Experimental Research of a Two-Dimensional Electron Gas on an InSb Surface MIS-structured samples are fabricated by first evaporating about a 170-nm-thick SiO2 C SiO insulating layer on a p-type InSb substrate by a photo-CVD method. Then use a lithographic technique to define an area and evaporate gold onto the insulating layer to form a gate electrode. Use deposited In metal as the back ohmic contact electrode and a conductive silver glue as the contact to the gate electrode to finish the structure. The electrode area is 9  104 cm2 . NAD from a Hall measurement is 2  1016 cm3 . Figure 4.30 shows the capacitance-voltage spectrum measured at various frequencies. It is seen from Fig. 4.30 that each capacitance spectrum curve has three rising regions as inversion occurs corresponding to onset voltages 2:4, 2:0, and 5.0 V marked V0 , VT , and V1 , respectively at the top of the figure. When an MIS device transitions from depletion into inversion electrons begin to fill the ground-state subband and the capacitance increases rapidly, a situation which corresponds to the rising region at onset voltage V0 in the figure, then the rate of rise of the capacitance begins to slow when the gate voltage increases to VT . This rising behavior is

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239

Fig. 4.30 Variable frequency C -V spectra of a p-type InSb MIS structure Table 4.3 Fitted parameters

i 0 1

ji 0.610 0.720

Ei0 (eV) 0.046 0.100

Ei1 .eV  cm2 / 1:50  1014 8:00  1014

Ei0 .eV  cm4 / 3:0  1027 2:0  1026

interpreted as being caused by electrons beginning to fill the first excited state. So the structure at VT is not caused by electrons filling only the ground-state subband. A more telling characteristic is that with an increase of the measurement frequency, the structure at VT gradually disappears and the capacitance increase gradually becomes more rapid. So we think that there exists an acceptor-type resonance defect state in the conduction band that captures electrons and leads to a reduction of the number of electrons that participate and make contributions to the capacitance. As a result, this slows the rate at which the capacitance rises. With an increase of measurement frequency, the probability of a defect state capturing an electron decreases, and the rate at which the capacitance rises gradually recovers. Fitting the low-frequency (300 Hz) experimental result to a nonquantum limited C -V model (using Table 4.3) is showed as the dashed curve in Fig. 4.31. In Fig. 4.31, the solid curve is an experimental result. The fit is not good near VT because the trap effect is not included in the fitting procedure. The parameters extracted from the fitting procedure are "s D 18, Eg D 0:206 eV, m0 D 0:014 m, Ci D 18:59 pF, E10 D 0:172 eV, VFB D 7:8 V, Vt0 D 2:4 V, and Vt1 D 5:0 V. Figure 4.32 shows the variations of the ground-state subband energy E0 , the first excited-state subband energy E1 , and the Fermi energy EF as functions of the electron concentration in inversion layer. There are two subbands that are filled with electrons. The ground-state os filled first at the onset of inversion, then the first excited-state begins to fill when the electron concentration in the inversion layer

240

4 Two-Dimensional Surface Electron Gas

Fig. 4.31 Fitted curve (solid curve) and experimental result (dashed curve) of the low-frequency C -V spectrum of a p-InSb MIS device

Fig. 4.32 The variations of the subband energy levels E0 , and Ei and the Fermi energy level as functions of the electron concentration in the inversion layer

increase to 9:4  1011 cm2 . The corresponding bias voltages are 2:4 and 6.0 V, and are responsible for the energy crossovers at voltages V0 and V1 in the spectrum that are marked by P1 and P2 in Fig. 4.32. The rate at which the Fermi level increases begins to decrease when it crosses the first excited subband state as electrons fill this state. As the net electron density in the inversion layer continues to increase, the Fermi level is gradually pinned near the bottom of one of the subband excited-states. When the electron concentration in the inversion layer increases from 0 to 1:58  1012 cm2 , the subband ground state and the first subband excited-state increase from 47.1 and 100.7 to 63.2 and 178.6 meV, respectively, whereas EF increases from 47.2 to 196.0 meV. Figures 4.33 and 4.34 show the variations of the subband bottom effective masses mi .Ei /=m .i D 0; 2/ and the subband electron penetration depths hZii with the electron concentration in the inversion layer, respectively. Figures 4.35 and 4.36 show the variation of the inversion layer average thickness zav and the depletion layer thickness Zd . P1 and P2 correspond to the places where the ground state and the first excited state begin to fill with electron. By careful observation, we find that, similar to the variations of Fermi level, the rate at which zav

4.3 Experimental Research on Subband Structures

241

Fig. 4.33 The variations of the subband bottom effective masses as functions of the electron concentration in the inversion layer

Fig. 4.34 The variations of the subband electron penetration depths as functions of the electron concentration in the inversion layer

Fig. 4.35 The inversion layer’s average thickness, zav , variation as a function of the electron concentration in the inversion layer

and Zd vary both slow when the first excited state begins to fill with electrons. These rates slow even more when electrons begin to fill higher level subbands. When the electron concentration in the inversion layer increases from 0 to 1:58  1012 cm2 , the inversion layer average thickness decreases from 16.1 to 6.4 nm, whereas the depletion layer thickness still increases from 148.9 to 191.8 nm. As a comparison, in Fig. 4.37, the solid curves are the variations of E10 .D E1  E0 / and EF 0 .D EF E0 / as functions of the electron concentration in the inversion layer, and the dashed curves are the theoretical result of Malcher et al (1987). From Fig. 4.37, we see that the experimental data and the theory for EF 0 agree well,

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4 Two-Dimensional Surface Electron Gas

Fig. 4.36 The depletion layer thickness, Zd , variation as a function of the electron concentration in the inversion layer

Fig. 4.37 A comparison between experimental (solid curves) and theoretical (dashed curves) for EF0 and E10 versus Ns (Malcher et al. 1987)

but the experimental data and the theory for E10 have a large discrepancy. The theory predicts that the third subband begins to fill when the electron concentration in inversion layer reaches 7  1011 cm2 , but the threshold concentration measured by experiment is about 9:4  1011 cm2 . The difference between the experimental data and the theory is probably caused by the adoption of a different parameter set. In their theory, they take some key parameters to be: T D 0 K, Eg D 0:235 eV, m0 D 0:0136 m, and NAD D 5  1016 .

4.4 Dispersion Relations and Landau Levels 4.4.1 Expressions for Dispersion Relations and Landau Levels Bychkov and R¨ossler have investigated theoretically the impact of the spin– orbit interaction on the surface electrons in narrow-gap semiconductor systems, in which the cubic term in k have also been taken in account (Bychkov and Rashba 1989; R¨ossler et al. 1989). The electron-subband dispersion relation and the main characteristics of the Landau levels were discussed qualitatively. The dispersion relation expressions and the energies of electron subband Landau levels in the inversion layer of p-type Hg1x Cdx Te have also been derived in subsequent papers

4.4 Dispersion Relations and Landau Levels

243

(Chu et al. 1990a, b). The physical quantities used in the expressions, such as the strength of the spin–orbit coupling, are obtained by fits to experiments. It is the first time these parameters have been determined quantitatively. The expressions can be used to describe qualitatively the zero-field spin splitting and the crossing of the Landau levels in the inversion layer of p-type Hg1x Cdx Te. From Kane’s nonparabolic model, the dispersion relation of the electron subband is given by: s   „2 k2 Eg;eff Eg;eff 2 C C Eg ; (4.67) E D  2 2 2m0 or s   „2 k2 Eg;eff Eg;eff 2 C ; (4.68) E D  C Eg;eff 2 2 2m .Ei / where Eg;eff is the effective band gap energy, Ei is the minimum value of the subband energy, m0 and m .Ei / are the effective masses at the conduction band edge and at E, respectively. The following relations are satisfied: Eg;eff D Eg C 2Ei ;   2Ei m0 : m .Ei / D 1 C Eg

(4.69) (4.70)

When the z-direction dependence of Ei is taken into account, Ei will be approximated by Ei;av , which is the average of Ei in the z direction. Equations (4.67) and (4.68) are derived from the eigenvalue equation without the spin–orbit coupling term, .rU  k/   . But the spin–orbit interaction plays an important role in the band structures of many materials. Also the spin–orbit interaction causes the electron-subband dispersion relations to acquire an addition part related to a large spin splitting at zero-magnetic field (Bychkov and Rashba 1984). In the absence of a magnetic field, we define the Hamiltonian including the spin–orbit term to be: 8 < H D H0 C „a  .k  "/; (4.71) k D .kx ; ky ; 0/; and : " D .0; 0; "z /: Here the second term of H is the spin–orbit or Bychkov-Rashba term, and ˛ is the spin–orbit coupling constant. The secular equation has the form: ˇ ˇ ˇ E  E i „˛"z k e i ˇ ˇ ˇ ˇi „˛"z k e i E  E ˇ D 0:

(4.72)

Then, with E given by (4.67) and (4.68), the solutions of (4.72) are:

E;

Eg;eff C D 2

s 

Eg;eff 2

2 C Eg

„2 k2 2m0

˙ „˛"z k :

(4.73)

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4 Two-Dimensional Surface Electron Gas

Here the symbol˙ denotes the different energies of the spin-split electron states (“”, “C”), and „˛"z is given by the relations: 8   2 eP 2 1 1 ˆ ˆ ˆ „˛ D ; and  < 3 Eg;eff Eg;eff Eg;eff C  ˆ 1 @V .z/ ˆ ˆ : "z .z/ D  : e @z

(4.74)

which depends on the strength of the spin–orbit coupling. The accurate value of the spin–orbit coupling strength is approximated by an average over the electron distribution function. It follows from (4.73) that the energy dispersion in narrowgap semiconductors splits into two branches even without a magnetic field present, and that the zero-field spin splitting energy is given by the strength of spin–orbit coupling. If a magnetic field B is applied parallel to kz , the contribution from the in-plane motion to the subband energy becomes quantized in units of the cyclotron energy and Landau levels are formed. In a system where the spin–orbit coupling is included, each Landau level splits into two nonspin-degenerate subbands with spin quantum number of s D ˙1=2. The energy eigenvalues of the nth Landau level without a spin–orbit coupling are given by:

0 En;˙

Eg;eff C D 2

s 

Eg;eff 2

2

    1  1 ˙ g b B C Eg „!c n C 2 2

(4.75)

If we treat the spin–orbit coupling term as a perturbation, then the Hamiltonian becomes  p  H1 iA n p ; (4.76) H D iA n H2 p where A D 2=C „˛"z , C is the cyclotron radius, H1 and H2 are ground-state Hamiltonians of the electron subband in a magnetic field but without a spin–orbit coupling term included. From this perturbation theory, the energy eigenvalues are

n; En1;C D

0 0 En1;C C En;

2

s  ˙

0 0  En1;C En;

2

2 C An:

(4.77)

The corresponding wave functions of the electronic states are given by: 8 ˆ ˆ ˆ ˆ < ˆ ˆ ˆ ˆ :

s

s p p 1C 1Cc 1 C 1 C c p p jn; i C i jn  1; Ci: n; D c 2 s1 C c s2 1 C p p 1C 1Cc 1 C 1 C c p p jn  1; Ci C i jn; i n1;C D 2 1Cc 2 1Cc

(4.78)

4.4 Dispersion Relations and Landau Levels

Here we define: c

4An : .En;  En1;C /

245

(4.79)

Equations (4.77) and (4.78) give the energy of the nth spin-split Landau level and the corresponding wave functions of their ground-state subbands in the inversion layer of a narrow-gap semiconductor. From (4.77), a zero-field spin splitting can change the position of the nonspin-degenerate Landau level in a magnetic field. It causes the En; branch to move up, but the En1;C branch to move down. Consequently, these two branches intersect one another at some magnetic field, which can be observed in magneto-transport measurements. The value of the magnetic field, at which the En; and En1;C branches intersect, is determined by the strength of the spin–orbit coupling. So the spin–orbit coupling can be determined from the effect of the observed intersection. Figure 4.38 shows SdH oscillation results measured at different magnetic fields. The oscillation maxima appear when the nth spin-split Landau level passes through the Fermi level. Figure 4.39 illustrates the magnetic-filed dependence of the gatevoltage spacing between the peaks 0 to 1C and 1 to 2C SdH oscillation curves. As the applied magnetic field decreases, the gate-voltage spacing Vg also decreases (Fig. 4.39). The 0 and 1C branches intersect at a critical magnetic field, which can be obtained by extrapolating the gate-voltage spacing curve to the magnetic field at which Vg D 0. The values of magnetic field obtained, at which the

Fig. 4.38 The conductivity as a function of gate voltage in the inversion layer of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 / at different magnetic fields

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4 Two-Dimensional Surface Electron Gas

Fig. 4.39 The magnetic-filed dependence of the gate-voltage spacing between the peaks, 0 to 1C and 1 to 2C

branches 0 and 1C , and 1C and 2C intersect, are 1.25 T and 2.35 T, respectively. The concentration, Ns , at a spin-split Landau level is given by the expression 2:4  1010 B.T / cm2 . Therefore, the energy of the spin-split Landau level that passes through the Fermi level is obtained from the Fermi energy EF versus Ns relation. On the contrary, we can calculate the energy of the nth spin-split Landau level from (4.77) if the parameter „˛"z is selected appropriately. This selection is made such that the magnetic fields, for which the intersection of the branches 0 and 1C , and 1 and 2C occur, are the same as those from the measured SdH oscillations. As a result, the energy spacing of the Landau levels is also consistent with the results from cyclotron resonance measurements. Chu et al. (1990a) have measured the cyclotron-resonance spectra in the inversion layer of p-type Hg1x Cdx Te (x D 0:234) at different electron concentrations. Figure 4.40 shows the results with photon energies of 12.7 and 17.5 meV. The calculated energy of the spin-split Landau levels is shown in Fig. 4.41 as a function of the magnetic field. The dotted-line and solid-line arrows show the electron transitions between the spin-split Landau levels with energy spacings of 12.7 and 17.5 meV, respectively. The photon energies for the indicated transitions are found to be the same in cyclotron resonance measurements. As shown in Fig. 4.42, as the electron density increases from 0 to 8  1011 cm2 , the value of „˛"z required to fit this data only changes from 8  109 to 6  109 eV cm. The effective energy gap is also shown in Fig. 4.42 as a function of the electron concentration. From the values deduced for Eg;eff and „˛"z , the dispersion relation of the spinsplit subbands can be obtained from (4.73), and are shown in Fig. 4.43. The energy difference between E and EC is about 25 meV at k D 2  106 cm1 . The energy minimum of the branch “C” does not occur at k D 0 but rather at k D 4  105 cm1 , and its minimum value is 1 meV. Because of the spin–orbit interaction, the dispersion relation splits into two branches in the inversion layer of narrow-gap semiconductors even without a magnetic field.

4.4 Dispersion Relations and Landau Levels

247

Fig. 4.40 Cyclotronresonance spectra of a p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 / at different surface electron concentrations with photon energies of 12.7 meV (doted curves) and 17.5 meV (solid curves)

4.4.2 Mixing of the Wave Functions and the Effective g Factor From (4.78), the wave functions of the antiparallel-spin electrons belonging to neighboring Landau levels are mixed. So the wave function of §n; includes two components jn;  > and jn  1; C >, and §n1 ; C is a combination of the wave functions jn  1; C > and jn;  >. According to (4.78), §n; and §n;C can be expressed as: 8 <

n;

:

n;C

q 2 jn  1; Ci 1  cn; q : 2 D cn;C jn; Ci C i 1  cn;C jn C 1; i D cn; jn; i C i

(4.80)

Figure 4.44 is a plot of the mixing factors, jCn;˙ j2 , as a function of the magneticfield for several of the Landau spin-split levels in the inversion layer of p-type Hg1x Cdx Te (x D 0:234, NA D 4  1017 cm3 ). Except for the level 0 , the wave functions §n;˙ are composed of two parts jn; ˙i and jn ˙ 1; ˙i . The rate of increase of the mixing factors slows as the order, n, of the Landau level increases, and it is weakened for all n as the magnetic field increases.

248

4 Two-Dimensional Surface Electron Gas

Fig. 4.41 Energy of the spin-split Landau levels in the inversion layer as a function of magnetic field of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 / (the arrows show the magnetooptical-induced electron transitions between different spin-split Landau levels) Fig. 4.42 Effective band gap energy and spin–orbit coupling strength as a function of the electron concentration in the inversion layer of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 /

Equation (4.80) indicates that theoretically an electron can transition between the spin resonance states §n; and §n;C . There are two transition paths possible. One is a transition between the states jn; Ci ! jn; i, related to a normal spin resonance, and in this case results from mixing conduction band and valance band wave functions. It has the same origin as the spin resonance in bulk materials. The others are the transitions jn; Ci ! jn  1; Ci or jn C 1; i ! jn; i. In essence,

4.4 Dispersion Relations and Landau Levels

249

Fig. 4.43 The dispersion relations of the spin-split subbands in p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 /

Fig. 4.44 The mixing factors in the inversion layer of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 /

the last one is related to the cyclotron resonance with n D 1, and it is a new feature of spin resonance when the spin-split Landau levels form in semiconductor systems. Figure 4.45 shows how the mixing of the wave functions enables different transitions among the spin-split Landau levels. Sizmann et al. (1988) were the first to report the spectra of electron-cyclotron resonance in the narrow-gap semiconductors. Since the signal of the spin resonance is 20 times weaker than that compared with cyclotron resonance, it is difficult to detect. But the spin resonance signal can be observed in the cyclotron-resonance-inactive mode if we change the direction of the magnetic field in a cyclotron resonance measurement. Figure 4.46 shows the cyclotron-resonance and spin-resonance spectra in the inversion layer p-type Hg1x Cdx Te with a photon energy of 17.6 meV. The resonance peak results from the electronic transition from state 2C ! 3C . With

250

4 Two-Dimensional Surface Electron Gas

Fig. 4.45 The mixing of wave functions enables different transitions among spin-split Landau levels. Some permitted transitions are indicated by dotted lines

Fig. 4.46 Cyclotronresonance and spin-resonance spectroscopy on the inversion layer of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 /

an electron concentration increase, the Fermi level moves to a higher energy and the peak moves to the high-magnetic-field side of the spectrum. As the electron concentration changes from 3  1011 to 4:6  1011 cm2 , the spin-resonance peak approaches the cyclotron-resonance peak from the high-magnetic-field side, which results from the intersection of the Landau levels. Figure 4.47 shows the energies of the Landau levels as a function of the magnetic field. The levels 2 and 3C intersect at 4 T. The spin-resonance peak of 2C ! 2 and the cyclotron-resonance peak of

4.4 Dispersion Relations and Landau Levels

251

Fig. 4.47 Landau level energies in the inversion layer of p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 / as a function of magnetic field

Fig. 4.48 Spin-resonance spectra for p-type Hg1x Cdx Te with x D 0:234 and NA D 4  1017 cm3 at different surface electron concentrations

2C ! 2C approach one another as the Fermi level moves to higher energy. The observed spin resonance confirms the wave function mixing and the intersection of the Landau levels. Figure 4.48 shows the spin-resonance spectra in the inversion layer of p-type Hg1x Cdx Te (x D 0:234, NA D 4  1017 cm3 ) with the photon energy set at 12.7 meV. For an electron concentration of NS D 2:11011 cm2 , the Fermi energy is 26.5 meV above the ground state, and the resonant peak is related to the transition,

252

4 Two-Dimensional Surface Electron Gas

Fig. 4.49 Effective g factor of the nth Landau level in p-type Hg1x Cdx Te .x D 0:234; NA D 4  1017 cm3 /

1C ! 1 . For an electron concentration of NS D 3:61011 cm2 , the Fermi energy is 42 meV above the ground state, and the resonant peak is relate to the transition, 2C ! 2 . These two kinds of transitions are illustrated in the diagram of the Landau level energies (the dotted curves in Fig. 4.41). The effective g factor is defined by: jg  j

.En;  En;C / : b B

(4.81)

According to (4.77), due to the spin–orbit interaction, the energy level En; shifts up but En;C shifts down. Consequently, the effective g factor is increased in semiconductor systems by the spin–orbit interaction. From (4.81), the effective g factor decreases as the magnetic field increases. Figure 4.49 shows the magnetic-field dependence of the effective g factor for the nth Landau level of the ground state in the inversion layer of p-type Hg1x Cdx Te. The solid curves are calculated results for n D 0; 1; 2; 3, and the triangular points are the measured results for n D 1; 2. These results for the spin resonance clearly indicates that the spin–orbit interaction has an important effect on the subband structures of narrow-gap semiconductor surface layers.

4.5 Surface Accumulation Layer In the preparation of an Hg1x Cdx Te photoconductive detector, surface passivation is usually needed. The passivation layer contains two parts: a prime insulating layer (anodic oxidation, anodic sulfideadation, or anodic fluorination) and then covered with a ZnS layer. A potential well and a large number of active defects are introduced into the surface in these complicated chemical processes (Nemirovsky

4.5 Surface Accumulation Layer

253

and Kirdron 1979). Also band bending occurs on oxidation of an exposed surface of Hg1x Cdx Te (Nimtz et al. 1979). Because of these two effects, an accumulation layer or even an inversion layer is formed at the surface. The surface electron concentration of an Hg1x Cdx Te photoconductive detector is 1011 –1012 cm2 , which often makes the surface potential larger than the bandgap of the material. In addition, a typical value of the thickness of a photoconductive detector is 10 m, and the carrier concentration is 1014 –1015 cm3 at 77 K. The net number of surface carriers is the same as that of the bulk or even larger, so the surface condition has an important influence on device performance. The electron concentrations, effective masses, and energy levels in different subbands of an accumulation layer can be calculated from the WKB approximation. In a SdH oscillation experiment for an n-Hg1x Cdx Te accumulation layer, the electron concentrations for different subbands are gleaned from a Fourier analysis of the SdH oscillation curves. Furthermore, the electron concentration and mobility can be learned from the mobility spectrum. Nemirosky and Kidron (1979) obtained electron concentrations and mobilities of an Hg1x Cdx Te accumulation layer from Hall Effect and capacitance-voltage measurements. After measuring the SdH oscillations of an accumulation layer, Nicholas et al. (1990) pointed out that a heavily accumulated surface layer of Hg1x Cdx Te could be described as a 2DEG containing several subbands. A theoretical calculation of the dispersion relations of these subbands depends on a self-consistent treatment of the surface potential and the surface electron concentration. Nachev (1988) and Lowney et al. (1993) applied an eight-band model to calculate the dispersion relations of the different subbands in a surface accumulation layer and an inversion layer, but the computational complexity of the model is quite high. Ando (1985) used a simpler semiclassical approximation to study the electronic properties of subbands in surface accumulation layers of narrow gap semiconductors.

4.5.1 Theoretical Model of n-HgCdTe Surface Accumulation Layer The conduction band of Hg1x Cdx Te is nonparabolic. The Kane model can be rewritten as:   Ek „2 k 2 D ; (4.82) Ek 1 C Eg 2m0 where k D .kx ; ky ; kz / is the three-dimensional wave vector, Ek is the electron energy at k, the wave vector, Eg and m0 are the bandgap of the material and the effective mass at the conduction band edge, respectively. The electric potential distribution of a heavily accumulated surface layer of an Hg1x Cdx Te device follows the Poisson equation: d2 V .z/ .z/ en.z/ D D ; dz2 "s "0 "s "0

(4.83)

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4 Two-Dimensional Surface Electron Gas

where s is the low-frequency dielectric constant, and n.z/ is the electron concentration, which is mainly due to the ionized active surface impurities. Bulk ionized impurities, and the image force caused by different dielectric constants of the layers between the bulk and the surface, have less influence on the electric potential than the surface impurities. Thus, their effect is neglected in (4.83). For a low-temperature case, a semiclassical approximation, and spin degeneracy, the electron concentration can be written as: n.z/ D

2 4 KF .z/3 : .2/3 3

(4.84)

The Fermi wave vector KF as a function of position z has the following relation:   „2 .k 2 C kz2 / „2 KF2 EF  eV .z/ : D D ŒE  eV .z/ 1 C F 2m0 2m0 Eg

(4.85)

where now k 2 D kx2 C ky2 . In the limiting condition, „ ! 0, classical mechanics replaces quantum mechanics. The nature of the WKB approximation (Messiah 1959; Bohm 1954) is to introduce a series expansion in „ and ignore the third and higher order terms. Therefore, we can replace the Schr¨odinger equation with its classical limit. Because this method is useful in a regime beyond the usual classical explanation (e.g., the regime where E < V ), it is applicable over a wider scope than expected for a classical approximation. We use the WKB approximation to calculate the energy levels in a quantum well of Hg1x Cdx Te formed by a surface accumulation layer. The subband energy of surface accumulation layer En .k/ and the normal surface wave vector, kz , follow from the expression: Z

zn 0

  3 ; kz dz D n C 4

(4.86)

where zn is the turning point defined by kz Œzn ; k; En .k/ D 0. The only difference between (4.86) and Bohr-Sommerfeld (Eisberg and Resnick 1985) quantum law is that a fractional quantum number replaces an integer quantum number. From (4.82–4.86), we obtain: Z

EF  .k/

d Œ˛F .; Eg /1=2



    EF C En .k/ ˇŒ  EF C En .k/ 1 C Eg   3 1=2 k 2 ; (4.87) D nC 4

where ˛D

2e.2m0 /3=2 ; 3 2 "s "0 „3

(4.88)

4.5 Surface Accumulation Layer

255

ˇD

2m0 ; „2

(4.89)

 D EF  eV .z/;

(4.90)

  „2 k 2    EF C En .k/ D Œ   EF C En .k/ 1 C ; Eg 2m0

(4.91)

and

Z



dŒ.1 C =Eg 3=2 :

F .; Eg / D

(4.92)

0

From (4.87), given k D kFn and En .k/ D EF , we can calculate the Fermi wave vector of the nth subband kFn and the electron concentration of the nth subband 2 =, where the sum over n of Nsn is Ns . Normally, according to the clasNsn D kFn sical theory, the surface electron concentration Ns0 is nearly the same as the sum of the subband electron concentrations Ns . Ns0 can be calculated from the surface potential distribution: Ns0

ˇ "s "0 dV .z/ ˇˇ "s "0 Œ˛F .EF ; Eg /1=2 : D D e dz ˇzD0 e

(4.93)

The effective mass of the nth subband is defined as: 1 1 @En .k/ : D 2  mn „ k @k

(4.94)

and it can be obtained by solving (4.87).

4.5.2 Theoretical Calculations for an n-HgCdTe Surface Accumulation Layer The concentration x of an Hg1x Cdx Te material, selected to produce an 8–14 m wave band photoconductive detector, is approximately 0.2. From the CXT formula (Chu 1985b; Chu et al. 1982, 1983), we obtain Eg D 93:45 meV, m D 8:02  103 m0 , for T D 1:2 K, and the dielectric constant at low frequency is s D 17:6 (Yadava et al. 1994). Gui et al. (1997) calculated the surface accumulation layer subband parameters for two n-Hg1x Cdx Te photoconductive detectors, with x D 0:214 and 0.191. Figure 4.50 shows the relation between Ns and energy at the bottom of the different subbands, En .k D 0/. The Fermi level is pinned at the donor level. It is generally agreed that shallow donor levels in Hg1x Cdx Te overlap the bottom of the conduction bands in the vicinity of x D 0:2. From Figure 4.50, we see that En decreases as Ns increases. Figure 4.51 shows the electron concentration of the nth subband Nsn and the classical surface electron concentration NS0 as a function of Ns . These functions

256

4 Two-Dimensional Surface Electron Gas

Fig. 4.50 Theoretically calculated relations between Ns and the energy En at the bottom of Hg1x Cdx Te surface subbands

Fig. 4.51 Theoretically calculated electron concentrations of surface subbands for Hg1x Cdx Te detectors with different x values

are calculated in the heavily accumulated surface layers of long-wavelength photoconductive detectors with x D 0:214 and 0.191. In Fig. 4.51, it shows that Ns is about 20% higher than NS0 . Calculations of heavily accumulated layers of Hg1x Cdx Te detectors having different compositions .x D 0:191–0:214/, demonstrate that the relation between Nsn and Ns are linear and nearly independent of composition x. The slope changes from the ground state to the fourth excited state are 0.668, 0.219, 0.077, 0.027 and 0.009, respectively. Lowney et al. (1993) applied

4.5 Surface Accumulation Layer

257

Fig. 4.52 Predicted relation between effective masses at the bottom of the different subbands m n vs Ns for an Hg1x Cdx Te detector

the eight-band model to analyze the heavily accumulated layer of a Hg1x Cdx Te detector .x D 0:191/. For n D 0–3, the slopes are 0.673, 0.223, 0.077, and 0.027, respectively. J. Singleton et al. (1986a) analyzed a lot of experimental results of n-Hg1x Cdx Te materials, for band gaps ranging from 30–90 meV, and obtained similar results. For n D 0–4, the slopes of Nsn .Ns / in an accumulation layer are 0.6452, 0.2158, 0.097, 0.032, and 0.010. From these facts, we reach the conclusion that the gross carrier concentration of an n-Hg1x Cdx Te accumulation layer can be calculated based on the carrier concentration of any subband. Moreover, the carrier concentration of any subband can also be calculated knowing the gross carrier concentration of the accumulation layer. Figure 4.52 shows the gross surface carrier density dependence of the effective masses at the bottom of the different subbands. From the figure, we see that the effective mass of the ground state is the largest, and the effective mass decreases with increasing subband index. A qualitative explanation is based on(4.11), and the physical reason is that the energy of the nth subband E0n is higher than the energy of ground-state E0 , as well as wave function diffusion Z0n > Z0 ; therefore, mn is smaller than the effective mass of the lowest subband.

4.5.3 Experimental Results for n-HgCdTe Surface Accumulation Layers Gui et al. (1997) measured the transport properties of the two samples discussed above. The dimensions of the two samples were both 888 m  290 m  8 m, the distance between the Hall electrodes was 336 m, the top and bottom surfaces of samples were passivated by anodic oxidation, and extended In electrodes

258

4 Two-Dimensional Surface Electron Gas

formed good ohmic contacts between the electrodes and the samples. At T D 77 K, the carrier concentration and mobility of the bulk material are approximately 5:0  1015 cm3 and 2:0  105 cm2 =Vs. In order to accurately measure the SdH oscillations, the measurement system was automatic. It comprised a high precision digital current source and programmable digital voltmeter. In the range from 1.2–50 K, samples were measured by a DC method in a high magnetic field with tilt angles between the magnetic field direction and the sample’s surface that were 0ı ; 15ı ; 90ı : : :. (A 0ı tilt angle means that the magnetic field direction is perpendicular to the sample’s surface, whereas a 90ı tilt angle means that the magnetic field direction is parallel to the sample’s surface).

4.5.4 Results of an SdH Measurement Figure 4.53 shows the dependence of the magneto-resistance at T D 1:2 K on the tilt angle of magnetic field. Samples exhibited complicated SdH oscillations at tilt angle,  D 0ı , and SdH oscillations were found at low magnetic fields at tilt angle,  D 90ı . Because the bulk electron concentration is approximately 1014 –1015 cm3 and the Fermi level is near the bottom of the conduction band, the SdH oscillations induced by the bulk carrier concentration could be found only at low magnetic fields. The two-dimensional property of the oscillations is proven by the fact that a peak marked by arrows in Fig. 4.53 drifts as the tilt angle varies. The SdH oscillations are complicated and are not a periodic function of 1/B with a fixed period, but

Fig. 4.53 SdH oscillations of sample A for different tilt angles. (a) 0ı tilt angle means the magnetic field direction is perpendicular to the sample’s surface; (b) the arrows denote corresponding peaks of the SdH oscillation that drift with a variation of the tilt angle, showing the two-dimensional property of the oscillations

4.5 Surface Accumulation Layer

259

Fig. 4.54 The drift of a peak of the SdH oscillation with a variation of the tilt angle. The dependence of this peak on cos  proves that oscillations are caused by two-dimensional carriers

Fig. 4.55 The magnetic field intensity dependence of the Hall voltage and the magneto-resistance. (a) sample A; (b) sample B

rather a combination of several oscillation types with different periods. Because the oscillation period of a given carrier type is dependent on its concentration, the sample contains multiple carrier types. Assuming that the Fermi level is not related to the tilt angle of the magnetic field, the tilt angle dependence of the SdH oscillatory peak’s migration, marked by arrows in Fig. 4.53, is shown in Fig. 4.54. There is a cosine relation between the two parameters. Figure 4.55a and b shows the magnetic field intensity dependence of the Hall voltage and the magneto-resistance. The tilt angle of the magnetic field was set at 0ı , and the current applied to the samples was 2 mA. The oscillations in the figures weakened gradually and finally disappeared when the tilt angle changed from 0ı to 90ı . This fact shows that oscillations are caused by the surface accumulation layer and have a two-dimensional property. When the applied magnetic field is perpendicular to the device’s surface accumulation layer, the subband splits into a series of Landau levels. By varying the magnetic field, the Landau levels move through the Fermi level that changes the density of electronic states and causes magnetoresistance oscillations. The minimum magneto-resistance oscillation corresponds to a Hall voltage plateau. Every subband causes a series of oscillations and their periods are related to 1/B. The relation between n and Pn is n D 4:82  1010 Pn .cm2 /, where Pn is the fundamental frequency of oscillation of the nth subband.

260

4 Two-Dimensional Surface Electron Gas

Fig. 4.56 Fourier transformation curves of SdH oscillations for samples A and B Table 4.4 Surface electron concentrations for different subbands of samples A and B B1 .T/ B2 .T/ B3 .T/ Ns0 .1012 cm2 / Ns1 .1012 cm2 / Ns2 .1012 cm2 / 0 A Surface 46.8 24.4 9.12 2.25 1.17 0.437 Surface00 31.9 15.0 3.75 1.53 0.72 0.181 36.1 10.1 3.31 1.73 0.485 B Surface0 68.9 26.4 3.28 2.68 1.27 0.157 Surface00 55.8

Fig. 4.57 Relations between the net electron concentration and the electron concentrations of the subbands (dots are plotted from the data in Table 4.4 and the solid lines are linear fitted results)

From Fourier transformations of the SdH oscillation curves, we can obtain the electron concentrations of the different subbands. Figure 4.56 shows the Fourier transform curves of SdH oscillations for samples A and B, The different surfaces are labeled by symbols .0 / and .00 / respectively. Table 4.4 shows the surface electron concentrations for different subbands calculated from Fig. 4.56. The relations among the electron concentrations for different subbands are not predicted well by the theory of Sect. 4.2. The main problem is that value of Ns1 =Ns0 is less than its theoretical value. This is because SdH oscillations are complicated processes and(4.87) is just an approximation. Even so, according to the data in Table 4.4, the fitted lines for Ns0 –Ns and Ns1 –Ns (Fig. 4.57) are linear and pass through the origin, which proves that there is some merit to the approximation behind (4.87). Thus, approximate carrier concentrations for the different subbands in the two-dimensional system can be obtained from fits to the SdH oscillation measurements.

4.5 Surface Accumulation Layer

261

Fig. 4.58 QMS for sample A at different temperatures: (a) 1.2 K and (b) 35 K

Gui et al. (1998) studied these samples by using a quantitative mobility spectrum (QMS) analysis. Figure 4.58a and b shows the QMSs of sample A at T D 1:2 and 35 K. The exact carrier mobilities and the concentrations of different subbands in these samples can be obtained at T D 35 K because the SdH oscillations almost disappear at this temperature. Three peaks in Fig. 3.5.9b correspond to the mobilities of the bulk electrons, the two-dimensional electrons of the top, and bottom surface accumulation layers, respectively. The electron mobilities at 35 K for different subbands for the same surface are equal for sample A. The QMS is obviously more complicated at 1.2 K, compared with that at 35 K, because then the electron mobilities of different subbands in the surface two-dimensional electron systems are different. Ionized impurity scattering plays a predominant role at 1.2 K. The electron effective masses of different subbands are different so the corresponding mobilities are different too, and the peaks from the different subbands are distinguishable in the QMS. At the increased temperature, for example at 35 K, many scattering mechanisms become effective, for example, ionized impurity scattering, polar optical phonon scattering, alloy scattering, and dislocation scattering. Because of the different kinetic energies of the subbands, each scattering type plays a different role and the net effect is that the differences among the electron mobilities for different subbands tend to be reduced. Table 4.5 shows the concentrations of various electrons obtained from a QMS analysis, an SdH oscillation measurement, and theoretical calculations. Results of the QMS analysis at 35 K are the bulk electron concentration is 2:14  1014 cm3 , the electron concentrations at the top and bottom surfaces are 4:31  1012 and 3:25  1012 cm2 , respectively. The same results at 1.2 K are 2:20  1014 , 4:11  1012 , and 3:03  1012 cm2 , which agree with the results at 35 K. In addition, the electron distributions of different subbands, obtained by QMS analysis, are in accord with the theoretically predicted distributions. So the results from the QMS measurements agree with theory better than those from SdH oscillation measurements. The electron relaxation times for different subbands in an Hg1x Cdx Te surface accumulation layer differ due to the differences among their electron effective

262

4 Two-Dimensional Surface Electron Gas

Table 4.5 Magneto-resistance data fits for two kinds of carriers at 1.2 K Sample 1 .cm2 =V s/ 2 .cm2 =V s/ N1 .cm3 / N2 .cm3 / 5 4 14 D685–7 2:65  10 3:12  10 7:70  10 2:44  1015 5 4 15 D685–5 2:23  10 2:18  10 8:10  10 5:08  1015

B1 .T/ 0.034 0.06

B2 .T/ 0.3 0.54

Fig. 4.59 The QMS of sample B at different temperatures

masses, kinetic energies, and subband wave functions. In order to study the temperature dependence of the subband electron mobilities in an Hg1x Cdx Te surface accumulation layer, we analyze the QMS experiment data in a variable magnetic field at different temperatures. Figure 4.59 shows the QMS of sample B, from which we find the dependence of the subband mobility on temperature. At 1.2 K, there is a great difference between the electron mobilities of three subbands in surface .0 /, but the electron mobilities of the subbands are almost the same for surface .00 /. This is because the net electron concentration of surface .0 / is 51015 cm3 , but only 51014 cm3 for surface .00 /. According to a theoretical calculation, there is little difference between the electron mobilities of subbands when the electron concentration is low and only the ground state has an appreciable occupancy; however, the effective mass of the ground state is more than two times that of the second excited state and it becomes occupied when the electron concentration reaches 5  1015 cm3 . At low temperature, the electron mobility of the ground state .n D 0/ is the lowest, and the mobilities of the excited

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263

Fig. 4.60 (a) The temperature dependence of electron concentrations for sample B. (b) The temperature dependence of electron mobilities for sample B

states all progressively increase with increasing quantum index because their effective masses increase. With an increasing temperature, the electron mobilities of the excited states gradually decrease, and finally would be equal to the electron mobility of the ground state which is nearly independent of temperature. The temperature dependence of the electron concentrations and effective masses for sample B are shown in Fig. 4.60. From this figure, we see that the relationship between the temperature and net electron concentration are different for the two surfaces. The net electron concentration of surface .0 / varies very slowly with a temperature variation; but the net electron concentration of surface .00 / varies rapidly with a temperature variation. Physical mechanism differences between these two surfaces may explain these facts. One possible reason is that due to stress, defect states are introduced into the surface attached to the substrate. These donor defect states have a finite ionization energy, and ionize gradually as the temperature increases. From the relation: n / exp.ED =kB T /, we deduce an approximate ionization energy for these surface donors to be, ED D 3:1 meV.

4.6 Surfaces and Interfaces 4.6.1 The Influence of Surface States on the Performance of HgCdTe Photoconductive Detectors For Hg1x Cdx Te photoconductive detectors, most of the passivation processes will introduce a surface accumulated layer to reduce surface recombination velocities and 1=f noise, as well as to reduce the intrinsic resistance of the device (Fig. 4.61).

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4 Two-Dimensional Surface Electron Gas

Fig. 4.61 Sectional view of a typical Hg1x Cdx Te photoconductive detector

The importance of passivation layers on device performance has attracted much previous consideration (Kinch 1981) and continuous studies (Nemirovsky and Bahir 1989; Nemirovsky 1990; Nemirovsky 1979). Singh pointed out that, for a detector, the effective minority carrier lifetime is tied to the surface states, especially, the fast surface states and the surface potential (Singh et al. 1991). However, all the studies mentioned above were mainly aimed at a qualitative analysis. Here the two-dimensional character of an accumulation layer due to passivation is taken into account (Singleton et al. 1986c; Lowney et al. 1993) when the distribution of surface potentials is calculated using Fang and Howard’s variational method. To further illustrate the influence of passivation on device performance, the spacial distribution of photogenerated carriers and the voltage response of Hg1x Cdx Te photoconductive detectors are calculated using a one-dimensional model. There exist large numbers of bound positive charges in the passivation layer of an Hg1x Cdx Te photoconductive detector. The equivalent concentration of electrons is induced at the surface of bulk materials due to the existence of the bound positive charges. The induced electrons are regarded as a quasi-2DEG since they exist in a very thin layer adjacent to the surface. There have been a series of theoretical models proposed, including a single-band model and multiband models to calculate the dispersive relation of the 2DEG. All the models, to be accurate, should be based on the self-consistent solution of the Schr¨odinger equation in conjunction with the Poisson equation. Among those models, Fang and Howard’s variational method (Fang and Howard 1966) is relatively simple and practical. Since the electron concentration in the surface accumulation layer is much larger than that in the bulk, the surface potential VH and the bound positive charge density based on the Fang and Howard’s method obey the following correlation: VH D where b is defined as

 b

3NI e 2 ; 2"s "0 b

33mn e 2 NI 8"s "0 „2

(4.95)

1=3 :

(4.96)

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265

In this expression, mn is the effective electron mass, e is the electric charge, 0 is the vacuum dielectric constant, and s is the static dielectric constant. The static dielectric constant of Hg1x Cdx Te materials s (Yadava et al. 1994) depends on the Cd concentration x: "s D 20:8  16:8x C 10:6x 2  9:4x 3 C 5:3x 4 :

(4.97)

When the device is irradiated, the photogenerated carriers in the bulk will move toward the surface where radiative recombination can take place. The surface potential of an Hg1x Cdx Te accumulated layer is a barrier for holes and this surface barrier will prevent holes from moving toward the surface. This causes the actual surface recombination velocity to be reduced. The effective surface recombination velocity is (White 1981): Seff

  VH ; D S0 exp  kB T

(4.98)

where S0 is the surface recombination velocity for a flat band, kB is the Boltzmann constant, and T is the absolute temperature. Accumulation layers exist at both the upper and lower surfaces of HgCdTe photoconductive detectors. Assuming the upper surface is the same as the lower surface, the resistance of a photoconductive detector can be expressed as: RD

l 1 ; .Nb b C 2NI s =d /e wd

(4.99)

where l, w, and d are the length, the width, and the height of the photoconductive detector, respectively. Nb is the bulk electron concentration, ms is the mobility of the surface electrons, which is of the order of 104 cm2 =Vs at 77 K (Gui et al. 1997), b is the mobility of the bulk electrons, which can be determined by an expression proposed by Rosbeck et al. (1982). For an HgCdTe material with Cd content x, the mobility of the bulk electrons is about 1–3  105 cm2 =Vs at 77 K. The minority carrier lifetime is significantly affected by surface recombination. The actual net lifetime due to surface recombination is determined as follows: 1 1 1 1 2Seff : D C D C

net

b

s

b d

(4.100)

In (4.100), the influence of the surface potential on the surface recombination velocity is included. The effective surface recombination velocity in(4.98) is adapted for the calculation of actual net lifetime in (4.100). When a photoconductive detector operated in a constant current mode is irradiated by monochromatic light with wavelength , the voltage responsivity RV is:  Rv D

 hc





b E net qR l

 ;

(4.101)

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4 Two-Dimensional Surface Electron Gas

where E is the intensity of bias electric field, c is the velocity of light, h is Plank constant, and  is the quantum efficiency. Next investigate the influence of the surface bound charge on the performance of n type photoconductive detector devices, operated at 77 K, with a Cd content x of 0.214, a bulk lifetime of 10 ns to 10 ms, a doping concentration of 5  1014 to 5  1015 cm3 , and a mobility of surface electrons of 2  104 cm2 =Vs. The photosensitive area of the detector is 50  50 m2 , and it has a thickness of 8 m. The wavelength of the incident light is 10:6 m. The quantum efficiency is 0.6. The magnitude of bias electric field is 20 V/cm. The predicted dependence of the photoconductive detector resistance on surface bound charge is shown in Fig. 4.62. The surface accumulation layer induced by passivation is a high-conductivity region, which leads to a reduction of the device resistance. As shown in Fig. 4.62, the resistance of detectors changes with a surfacebound charge variation when the density of surface-bound charges is of the order of NI D 1011 to 1012 cm2 . At NI < 1011 cm2 , the resistance of detectors is almost independent of the surface passivation, and is determined primarily by the bulk electron concentration. While for NI > 1012 cm2 , the detector resistance is determined primarily by the concentration of surface electrons, and is almost independent of the bulk electron concentration. Figure 4.63 shows the predicted influence of the surface bound charge on the net lifetime net of detectors. When the value of NI is relative small, net increases rapidly with increasing NI , finally saturates at value b . The existence of surfacebound charge induces an electron accumulation layer at the surface of n type detectors. The accumulated layer leads to a band bending at the surface, resulting in electron traps, which serves as a potential barrier for minority carriers (holes). The barrier prevents the diffusion of photogenerated holes toward surface and slows the surface recombination velocity. As described in (4.96), the surface potential

Fig. 4.62 The resistance is shown as a function of the surface bound charge density NI , for photoconductive detectors with different doping concentrations Nb

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267

Fig. 4.63 The net lifetime

net is shown as a function of the density of surface bound charge NI , for devices with different surface recombination velocities S0

Fig. 4.64 The voltage responsivity Rv for devices with different dopant concentration Nb as a function of the concentration of the surface bound charge NI . The values of other parameters are S0 D 1000 cm=s and

b D 1 s

increases with an increase of the density of bound charges. When the density of bound charges NI is larger than 3  1011 cm2 , due to the very high surface barrier for holes that they induce, the photogenerated holes can hardly overcome the barrier to reach the surface. This insight is useful for improving the performance of detectors. Figure 4.64 shows the predicted dependence of the voltage responsivity on the concentration of bound charges with different bulk doping concentrations. The minority carrier lifetime is 1 s and the surface recombination velocity is 1000 cm/s for this high detectivity device. When the concentration of bound charge in the passivation layer exceeds 1011 cm2 , the surface potential reduces the surface recombination rate of photogenerated holes and improves the device performance. Once the concentration of bound charge exceeds 1012 cm2 , the conductivity of the surface heavy accumulated layer is promoted, resulting in a reduction of the intrinsic resistance and device performance. With a further increase of the bound charge concentration, the device performance is reduced very fast, especially for the devices with low doping concentrations. Figure 4.65 shows the predicted dependence of the voltage responsivity on the bound charge concentration with different surface recombination velocities.

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4 Two-Dimensional Surface Electron Gas

Fig. 4.65 The voltage responsivity Rv for devices with different surface recombination velocities S0 as a function of the concentration of surface bound charges NI . The values of other parameters are Nb D 5  1014 cm3 and b D 1 s

The device minority carrier lifetime is 1 s and the doping concentration is 5  1014 cm3 . As shown in Fig. 4.65, there exists a peak of the voltage responsivity curve when the concentration of bound charges is in the range of 1011 –1012 cm2 . The position of the voltage responsivity peak shifts to higher bound charge concentrations following an increase of the surface recombination velocity. The voltage responsivity maximum is directly determined by the surface recombination velocity. The smaller the surface recombination velocity is, the larger is the voltage responsivity maximum. When the bound charge concentration is larger than 61011 cm2 , the detector voltage responsivity is almost the same even if surface recombination velocity changes by two orders of magnitude. Indications are that device performance will be improved if the passivation process and the effective surface recombination velocity are selected properly. Figure 4.66 shows the dependence of the voltage responsivity on the bound charge concentration for detectors with different minority carrier lifetimes, b . The doping concentration is chosen to be 5  1014 cm3 and the surface recombination velocity is 105 cm=s for this calculation. When the surface-bound charge is less than 1011 cm2 , the performance of devices is predicted to be independent of the minority carrier lifetime. Thus, the effective lifetime net of devices is determined by the surface recombination velocity. When the surface-bound charge concentration is in the range of 1011 –1012 cm2 , the variation of the voltage responsivity Rv is very large. For devices with a long lifetime . b D 10 s/, the voltage responsivity Rv varies with NI by two orders of magnitude. The discussion above indicates that the performance of HgCdTe photoconductive detectors depends sensitively on the concentration of surface-bound charges induced by the passivation process. On the one hand, the surface-bound charges reduces the recombination rate by preventing the photogenerated holes from reaching the

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269

Fig. 4.66 The voltage responsivity Rv for devices with different minority carrier lifetimes b as a function of the bound charge surface concentration NI . The values of other parameters are S0 D 105 cm=s, Nb D 5  1014 cm3

surface, resulting in an improvement of device performance; on the other hand, the surface-bound charges reduce the net device resistance, resulting in a reduction of device performance. The concentration of surface-bound charge can be changed by selecting a proper passivation process, so device performance can be optimized.

4.6.2 The Influence of the Surface on the Magneto-Resistance of HgCdTe Photoconductive Detectors The technology related to photoconductive detectors is well established (Broudy 1981). However, the surface of HgCdTe oxidizes easily allowing an nC type accumulated or inversion layer with high conductivity to form, which affects device performance. An anodic oxidation process is adopted to reduce the surface recombination velocity and 1=f noise. However, as we have seen this nC type accumulated layer when not properly controlled also produces a high conductivity that degrades devices (Lowney et al. 1993). A photoconductive detector is a two-terminal device and it cannot satisfy at least four electrode requirement for a Hall measurement. Most methods used to analyze multicarrier systems, such as a multicarrier fitting procedure, a mixed conduction analysis (Meyer 1993; Antoszewski and Faraone 1996), as well as a QMS analysis (Dziuba and G´orska 1992; Antoszewski et al. 1995; Meyer et al. 1995), are incapable of investigating the electrical characteristic of surface and bulk electrons in photoconductive detectors. A magneto-resistance measurement is regarded as an effective means to investigate semiconductors with complicated energy bands. It can also be used to estimate carrier mobilities. Conventional methods can only

270

4 Two-Dimensional Surface Electron Gas

be used to investigate single-carrier systems. However, prior to the work of Kim et al. (1993, 1995), they could not provide a solution to the multicarrier system due to the complexity of the magneto-resistance expressions. Kim et al. improved the magneto-resistance measurement technology, and developed a simplified model, named the reduced conductivity tensor (RCT) scheme, to reveal the transport properties of a multicarrier system. This section describes the experiments on photoconductive detectors in which the magnetic field is varied and the RCT scheme is used in the data analysis. The theoretical result is consistent with that obtained from experiments. The electron concentrations and mobilities of both the bulk and surface electrons as a function of temperature are also given in this section. Next the RCT scheme will be reviewed. The general procedure for the varying magnetic field data analysis using the RCT scheme is introduced in the papers by Kim et al. (1993, 1995). In the RCT method, only surface and bulk electrons that make the most significant contributions to the conductivity of photoconductive detectors are considered. The magneto-resistance M is defined as a function of magnetic field B: M.B/ D

.B/  .0/ ; .B/

(4.102)

where .B/ is the resistivity of sample at magnetic field B, and .0/ is the resistivity at B D 0. .B/ is defined in terms of the longitudinal component xx and the transverse component xy of the conductivity tensor: .B/ D

xx : 2 C xy

2 xx

(4.103)

The magneto-resistance M as a function of the conductivity tensor can be obtained by combining (4.102) with (4.103). Compared with other methods, RCT seems to be not very effective. However, the RCT method provides a unique way to obtain the carrier concentration and mobility for photoconductive detectors. This is because only the resistance as a function of magnetic field can be measured on these twoterminal photoconductive devices. Other potentially useful measurements, like the Hall voltage, cannot be accomplished on these structures. A system with J types of carriers is assumed when the RCT analysis is used. X.B/ and Y.B/ are relative values of the longitudinal and the transverse components of the conductivity tensor, respectively. They are defined as: X.B/

J X xx .B/ D Xj ; and xx .0/ j D1

J X xy .B/ D Y.B/

Yj : xx .0/ j D1

(4.104)

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271

For a system with two types of carriers, J D 2. In the more general case, for materials with good homogeneity, the number of carrier species is rarely more than three. However, for a sample with very poor homogeneity, it is asserted that there are an infinite number of carrier types existing in the system. The Xj and Yj defined in (4.104) satisfy the following equations: fj fj j B ; Yj D ; and 1 C .j B/2 1 C .j B/2 sj j N j qsj j Nj fj D P ; D s j j N j xx .0/

Xj D

(4.105)

where sj denotes the sign of the charged carriers, and has the same sign as that of its mobility j . sj D 1 denotes electrons, and holes are denoted sj D 1. fj is a dimensionless parameter that denotes the fractional contribution to the conductance of the j th carrier type under the no magnetic field condition. Nj and j are the concentrations and mobilities of the j th carrier types, respectively. q is the magnitude of electric charge. In an RCT process analysis, Nj is a dependent variable. When j and fj are given, the following expression is obtained: Nj D

fj xx .0/ qsj j

For a system with only one carrier type, fj D 1, Xj D 1=Œ1 C .j B/2 , and Yj D B=Œ1 C .j B/2 . For a system with multiple carrier types, the conditions 0 6 fj 6 1 and †fj D 1 must be satisfied because all carrier types make positive contributions to the conductance. From (4.102) to (4.105), we get: M.B/ D

X  1; X2 C Y 2

(4.106)

where the magneto-resistance is defined as a function of magnetic field, and depends on fj and j of each type of carrier. For a system with only two types of carriers, we have: .˛B/2 M.B/ D ; (4.107) 1 C .ˇB/2 p where ˛ f1 .1  f1 /, ˇ 1 =.  f1 /, and  .1  2 /= .1 C 2 /. When the magnetic field is low, one has M.B/ Š .˛B/2 / B 2 . For the case of a high magnetic field, M.B/ Š .˛=ˇ/2 , so M.B/ is independent of the magnetic field B, and only depends on the mobility and carrier concentration. Here the transition magnetic field regime is defined as B1 < B < B2 (B < B1 is the low magnetic field regime, and B > B2 is the high magnetic field regime). The transition width is:   B2 D 0:954; W D log10 B1 where M.B1 / D 0:1.˛=ˇ/2 and M.B2 / D 0:9.˛=ˇ/2 .

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4 Two-Dimensional Surface Electron Gas

Gui et al. (1997) measured the magneto-resistances of three HgCdTe photoconductive devices, and one HgCdTe film material grown by LPE. They analyzed the experimental data using a two-carrier -type RCT model. The fitted results are consistent with the experimental data. Often two types of carriers exist in HgCdTe photoconductive detectors, that is, bulk electrons and surface electrons induced by the surface passivation. The operating temperature of these detectors is generally lower than 77 K. In this case, the electrical properties of these detectors are significantly affected by the surface electrons. The mobility of the surface electrons is of the order of 104 cm2 =Vs. The surface electron contribution to the conductance is comparable with that of the bulk electrons. This occurs because of the high surface electron concentration, up to 1011 –1012 cm2 , though the surface electron mobility is one order lower than that of the bulk electrons. The Hg1x Cdx Te photoconductive detectors D685–6, D685–2 and D684–5 were prepared from bulk materials with a Cd concentration x of 0.214, dimensions of 888  290  8 m3 and having passivated surfaces. The magneto-resistances of D685–7 and D684–5 as functions of the magnetic field at 1.2 K is shown in Fig. 4.67. The solid and open symbols are experimental data and the solid curves are fits to the experimental results using a two-carrier-type model. The curves fit the experimental results well. The parameters determined from the fitting procedure are shown in Table 4.6. In Table 4.6, 1 and N1 are the bulk electron mobility and concentration, and, 2 and N2 are the surface electron mobility and concentration, respectively. In the RCT method, 2DEGs are considered to be homogeneously distributed across the whole thickness of the sample. Thus, the sheet concentration of surface electrons are found to be 1:92  1012 and 4:03  1012 cm2 for sample D685–7 and

Fig. 4.67 The magneto-resistance of two HgCdTe photoconductive detectors as a function of the magnetic field at 1.2 K. The solid and open symbols are experimental data and the solid curves are fits to the data. For sample D685–7: 1 D 2:65  105 cm2 =V s, 2 D 3:12  104 cm2 =V s, f1 D 0:73, and for sample D684–5: 1 D 2:23 105 cm2 =V s, 2 D 2:18 104 cm2 =V s; f1 D 0:86. WD is obtained from a calculation by inserting the parameters determined through the fitting process

4.6 Surfaces and Interfaces Table 4.6 Parameters determined by fitting the magneto-resistance data taken two-carrier-type model Sample 1 .cm2 =V s/ 2 .cm2 =V s/ N1 .cm3 / N2 .cm3 / D685–7 2:65  105 3:12  104 7:70  1014 2:44  1015 D685–5 2:23  105 2:18  104 8:10  1015 5:08  1015

273 at 1.2 K, using a B1 .T/ 0.034 0.06

B2 .T/ 0.3 0.54

Fig. 4.68 The experimental magneto-resistance data (solid symbols) and the fitted curve (dashed curve) carried out by a two-carrier-type model versus magnetic field for the sample LPE-1 at 77 K

D684–5, respectively, when the net concentration of surface electrons in Table 4.6 is multiplied by the thicknesses of samples. The contributions to the conductance from surface electrons for samples D685–7 and D684–5 are 27 and 14 . cm/1 , respectively. Indications are that surface electrons have significant effects on the device performance. In real HgCdTe detectors, there exist many other types of carriers, such as light holes and heavy holes, in addition to surface and bulk electrons. The mobilities of each carrier type are not unique, but can change with concentration and temperature. In particular, the nonparabolic energy bands encountered in HgCdTe also complicate its electrical properties. All the features mentioned above lead to some errors between the experimental results and the fitted curves. Even if the fits are nearly perfect the parameters extracted from them may be in error. Magneto-transport measurements can be used to investigate not only photoconductive detectors but also p-type HgCdTe materials prepared as photovoltaic devices. There always exist 2DEGs at the surface of HgCdTe materials prepared as photovoltaic devices. In Hall measurements, p-type HgCdTe materials with potentially excellent performance grown by LPE, are sometimes mistakenly regarded as n-type materials with bad performance. Figure 4.68 shows the experimental magneto-resistance data (solid dots) and the fitted curve (dashed curve) carried out by a two-carrier-type RCT model calculation versus magnetic field for the sample LPE-1 at 77 K. The sample LPE-1 is a p-type material with excellent performance grown by LPE. But the sample acts n-type due to the existence of surface electrons

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4 Two-Dimensional Surface Electron Gas

Fig. 4.69 For different types of carriers in the sample D685–2 at 77 K; (a) carrier concentration and (b) carrier mobility versus temperature

resulting in the hole contribution to the bulk conductance being only 7.5% of the total. However, the true information about the material’s behavior can be obtained by an RCT analysis. Transport measurements with a variable magnetic field were performed on sample D685–2 in the temperature range of 1.2–300 K. The carrier concentrations and mobilities of different types of carriers were investigated using an RCT analysis and the results determined are shown in Fig. 4.69. The curves in Fig. 4.69 were obtained after smoothing the experimental data. As shown in Fig. 4.69a and b, the bulk electron concentration almost does not vary as the temperature is elevated in the range from 1.2 to 100 K, while it rapidly increase with an increasing temperature beyond T > 100 K. The bulk electron mobility increases slowly with increasing temperature at low temperature, and reaches its maximum at about 35 K, and then decreases rapidly as the temperature continues to increase. The surface electron concentration and mobility are almost independent of temperature in the temperature range from 1.2 to 100 K, which is consistent with the behavior of the surface electrons in an n-type HgCdTe sample reported by Reine et al. (1993). The contribution to the net conductance from the surface electrons becomes progressively smaller compared with that from the bulk electrons as the temperature exceeds 100 K due to the rapid increase of the bulk electron concentration. Beyond 100 K, the surface electrons can be ignored. In that case (T > 100 K), it is fortunate that the surface electron contribution to the net conductance is small because their concentration and mobility determined by fitting experimental data using the RCT method are poorly given and are far from their actual values.

4.6.3 The Influence of Surfaces on the Magneto-Resistance Oscillations of HgCdTe Samples The transport characteristics of two-dimensional systems formed in surface accumulation layers also can be investigated by Shubnikov–de Haas (SdH) measurements

4.6 Surfaces and Interfaces

275

(Justice 1988). For Hg1x Cdx Te narrow band gap semiconductors, the quantum effect is very significant due to its small effective electron mass resulting in a large separation of Landau energy levels. The SdH phenomenon quantum transport mainly takes place at low temperature where the magneto-resistance of the degenerate semiconductor will oscillate with a variation of the magnetic field. In contrast to other measurement methods, the behavior of two-dimensional and threedimensional carriers can be distinguished by changing the angle between sample and magnetic field when the SdH measurement is performed. Besides, SdH measurements can be used to investigate the electron concentrations, effective electron masses, and scattering mechanisms (Chang et al. 1982; Koch 1982, 1984; Singleton et al. 1986a, b). In this section, the transport characteristics of a surface accumulation layer of an Hg1x Cdx Te photoconductive detector is investigated using a SdH measurement. The photosensitive surface area of the investigated sample is 2:5  105 –1:4  104 cm2 , and the sample thickness is 7–8 m. The upper and lower surfaces of the sample are passivated using the same process. The resistivity of sample S9601 as a function of magnetic field perpendicular to the sample’s surface at different temperatures are shown in Fig. 4.70. As shown in Fig. 4.70, the shape of the SdH oscillation varies little, but the magnitude of the oscillations decreases with increasing temperature. The SdH oscillations vanish when the magnetic field is parallel to the sample’s surface (except for a partial oscillation for the magnetic field in the range of 0 to 1 T at 12.5 K). The oscillations are not simply periodic in 1/B, which indicates that there exists more than one type of carrier. A fast Fourier transform (FFT) analysis can be used to extract the oscillation periods of the different carrier types. The results are shown in Fig. 4.71. Four peaks, 0, 1, 00 , and 10 can be distinguished at all the measured temperatures. It indicates that there are two subbands in each surface for this Hg1x Cdx Te photoconductive detector (0 and 1 denote one surface, 00 and 10 denote the other surface). The multiple subbands occupied by electrons are due to the small effective electron masses of the subband electrons resulting in

Fig. 4.70 The SdH oscillations of sample A with a thickness of 7 m as a function of magnetic field at different temperatures

276

4 Two-Dimensional Surface Electron Gas

Fig. 4.71 The FFT of the SdH oscillations for sample S9601 at different temperatures

Table 4.7 The electron concentration of each subband for sample S9601 at different temperature

Electron concentration .1012 cm2 / T (K) 1.5 2.0 3.4 12.5 20.5 45 55

0 0.40 0.41 0.36 0.43 0.37 0.44 0.41

1 0.57 0.54 0.53 0.57 0.53 0.61 0.62

00 1.53 1.50 1.46 1.54 1.50 1.58 1.66

10 1.93 1.87 1.82 1.92 1.82 1.94 1.96

a relatively low density of states. The sharp peak in the FFT at 12.5 K corresponds to a feature from the bulk electrons with a concentration of 5:2  1014 cm3 . The electron concentrations of different subbands extracted from the FFT analysis are shown in Table 4.7. It indicates that the electron concentration of each subband is independent of temperature.

4.6.4 The Influence of the Surface on the Correlation Between Resistivity and Temperature for an HgCdTe Photoconductive Detector The carrier concentration of each subband being independent of temperature at low temperature was demonstrated in Sect. 4.6.3. However, the concentration of intrinsic carriers in bulk materials will increase exponentially with increasing temperature, whereas the mobility variation trends of the surface and bulk electrons are the same,

4.6 Surfaces and Interfaces

277

so the contribution to the conductance from surface carriers will become progressively smaller as the temperature increases. Let’s treat a simple case, in which it is assumed that the concentration of surface electrons is independent of temperature for both the upper and lower surfaces of an Hg1x Cdx Te photoconductive detector. Then a three-band model (bulk, surface ground state, and excited-state electrons) can be used to fit the correlation between the resistivity and temperature. A proposed model for an Hg1x Cdx Te photoconductive detector following these assumptions is: .T / D

1 ; eŒnb .T /b .T / C 2ns0 .T /s0 .T /=d C 2ns1 .T /s1 .T /=d 

(4.108)

where nb .T /, ns0 .T /, ns1 .T / and b .T /, s0 .T /, s1 .T / are the concentrations and mobilities of the bulk electrons and the two types of surface electrons. The concentrations of the surface electrons are taken to be independent of temperature. The mobility of the bulk electrons is given by Parat et al. (1990) to be:  b D

1 1 C   1:9 300 Œme .300K/=me .T /.300=T /  b0

1 ;

(4.109)

me .300 K/ and 300 are the effective mass and mobility of the bulk electrons at 300 K. b0 is the asymptotic value of the mobility of the bulk electrons at very low temperatures. The mobilities of the surface electrons satisfy the following equations:  s0 D and

 s1 D

1 1 C b 0 1 1 C b 1

1 ;

(4.110)

:

(4.111)

1

0 and 1 are the asymptotic values of the surface electron mobilities at very low temperatures. The concentration of the bulk electrons satisfies the following equation: q .ND  NA / C .ND  NA /2 C 4n2i .x; T / : (4.112) nb D 2 0 , 1 , b0 , ns0 , ns1 , and ND  NA are the parameters found during the fitting process. The results fits the experimental data well if the subband surface electron concentrations extracted from the SdH measurement are selected as the initial values. Figure 4.72 shows comparisons of the fitted results to the experimental data for Hg1x Cdx Te photoconductive detector samples. As shown in Fig. 4.72, the theory fits the experimental results quite well. Table 4.8 collects the parameters extracted in the fitting procedure. In the surface accumulate layer, the mobility of ground-state electrons is smaller than that of the exited-state electrons. The magnitude of the ratio .0 =1 / 6 1 reflects the ratio of the effective masses of the ground-state electrons

278

4 Two-Dimensional Surface Electron Gas

Fig. 4.72 The resistivity of samples S9601 and S9608 is as a function of temperature. The symbols are the experimental data, the solid curves are the fitted results. The thicknesses of samples S9601 and S9608 are 7 and 8 m, respectively Table 4.8 The concentration and mobility of different types of electrons at very low temperature ND  NA ns0 ns1 b0 0 1 .1014 cm3 / .1012 cm2 / .1012 cm2 / .105 cm2 =V s/ .104 cm2 =V s/ .104 cm2 =V s/ S9601 4.52 4.24 1.34 3.21 4.52 6.56 S9608 9.1 2.68 0.91 3.25 5.03 6.81

and the excited state electrons, if their relaxation times are considered to be the same. It also indicates that the effective mass of ground-state electrons is larger than that of the excited state electrons. The curves in Fig. 4.72 are quite smooth, and it would be amazing if they could not be fit with the six adjustable parameters available! With this much latitude, the accuracy of the six parameters must be treated with caution.

References Amelio GF (1972) A new method of measuring interface state densities in mis devices. Surface Sci 29:125–143 Ando T (1985) Subbands in space-charge layers on narrow gap semiconductors: Validity of semiclassical approximation. J Phys Soc Jpn 54:2676–2681 Ando T, Fowler AB, Stern F (1982) Electronic properties of two-dimensional systems. Rev Mod Phys 54:437–672 Antoszewski J, Faraone L (1996) Analysis of magnetic field dependent Hall data in narrow bandgap Hg1x Cdx Te grown by molecular beam epitaxy. J Appl Phys 80:3881–3892 Antoszewski J, Seymour DJ, Faraone L, Meyer JR, Hoffman CA (1995) Magneto-transport characterization using quantitative mobility-spectrum analysis. J Electron Mater 24:1255–1262 Bohm D (1954) Quantum Theory. Constable, London

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Kim JS, Seiler DG, Colombo L, Chen MC (1995) Characterization of liquid-phase epitaxially grown HgCdTe films by magnetoresistance measurements. J Electron Mater 24:1305–1310 Kinch MA (1981) In: Willardson RK, Beer AC (eds) Semiconductors and Semimetals, Vol. 18. Academic press, New York, pp 313–384 Koch F (1975) In: Zawadzki W (ed) Narrow Gap Semiconductors. Springer-Verlag, Berlin Koch F (1982) In: Gornik E, Heinrich H, Palmetshafer L (eds) Physics of Narrow Gap Semiconductors, Vol. 152, Lecture Notes in Physics. Springer, New York, p 92 Koch F (1984) Two-dimensional systems, heterostructrues, and superlattics. In: Bauer G, Kuchar K, Heinrich H (eds) Solid State Science Series, Vol. 53. Springer, New York, p 20 Kuhn M (1970) A quasi-static technique for MOS C -V and surface state measurements. Solid State Electron 13:873–885 Lehovec K, Slobodskoy A (1964) Impedance of semiconductor-insulator-metal capacitors. Solid State Electron 7:59–79 Lowney JR, Seiler DG, Thurber WR, Yu Z, Song XN, Littler CL (1993) Heavily accumulated surfaces of mercury cadmium telluride detectors: Theory and experiment. J Electron Mater 22:985–991 Macdonald JR (1964) Distribution of space charge in homogeneous metal oxide films and semiconductors. J Chem Phys 40:3735–3737 Malcher F, Nachev I, Ziegler A, R¨ossler U (1987) Subband states in n-inversion layers on small-gap semiconductors. Z Phys B-condensed matter 68:437–444 Marques GE, Sham LJ (1982) Theory of space-charge layers in narrow-gap semiconductors. Surf Sci 113:131–136 Merkt U, Oelting S (1987) Simple description of nonparabolic two-dimensional subbands. Phys Rev B 35:2460–2462 Messiah A (1959) Mecanique quantique I. Dunod, Paris Meyer JR, Hoffman CA, Bartoli FJ, Arnold DA, Sivananthan S, Fauri JP (1993) Methods for magneto transport characterization of IR detector materials. Semicond Sci Technol 8:805–823 Meyer JR, et al. (1995) Advanced Magneto-Transport Characterization of LPE-Grown Hg1x Cdx Te by QMSA. MCT Workshop Nachev I (1988) Bound states in inversion layers on p-Hg1x Cdx Te: self-consistent results. Semicond Sci Technol 3:29–34 Nemirovsky Y (1990) Passivation with II–VI compounds. J Vac Sci Technol A 8:1185–1187 Nemirovsky Y, Bahir G (1989) Passivation of mercury cadmium telluride surfaces. J Vac Sci Technol A 7:450–459 Nemirovsky Y, Kirdron I (1979) The interface between Hg1x Cdx Te and its native oxide. Solid State Electron 22:831–837 Nicholas RJ, Nasir F, Singleton J (1990) High magnetic field characterisation of (Hg,Cd)Te surface layers. J Cryst Growth 86:656–666 Nicollian EH, Goetzberger A (1967) The silicon-silica interface–electrical properties as determined by the metal-insulator-silicon conductance technique. Bell System Technical Journal 46:1055–1133 Nimtz G, Schlicht B, Dornhaus R (1979) Long-term Hall-type conversion by vacancy diffusion in Hg1x Cdx Te at room temperature. Appl Phys Lett 34:490–491 Ohkawa FJ, Uemura Y (1974) Quantized surface states of a narrow-gap semiconductor. J Phys Soc Jpn 37:1325–1333 Reine MB, Maschhoff KR, Tobin SP, Norton PW, Mroczkowski JA, Krueger EE (1993) The impact of characterization techniques on HgCdTe infrared detector technology. Semicond Sci Technol 8:788–804 Rosbeck JP, Starr RE, Price SL, Riley KJ (1982) Background and temperature dependent currentvoltage characteristics of HgCdTe photodiodes. J Appl Phys 53:6430–6440 R¨ossler U, Malcher F, Lommer G (1989) In: Landwehr G (ed) High Magnetic Fields in Semiconductor Physics II. Springer, Berlin, p 157 Parat KK, Taskar NR, Bhat IB, Ghandhi SK (1990) Annealing and electrical properties of Hg1x Cdx Te grown by OMVPE. J Crystal Growth 106:513–523

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Scott W, Stelzer EL, Hager RJ (1976) Electrical and far-infrared optical properties of p-type Hg1x Cdx Te. J Appl Phys 47:1408–1414 Singh R, Gupta AK, Chhabra KC (1991) Surface passivation of mercury-cadmium-telluride infrared detectors. Def Sci J (India) 41:205–239 Singleton J, Nasir F, Nicholas RJ (1986a) High-magnetic field characterization of (Hg,Cd)Te detectors. Proc SPIE 659:99–108 Singleton J, Nicholas RJ, Nasir F, Sarkar CK (1986b) Quantum transport in accumulation layers on Cd0:2 Hg0:8 Te. J Phys C: Solid State Phys 19:35–42 Sizmann R, Chu JH, Wollrab R, Koch F, Ziegler J, Maier H (1988) In: Zawadzki W (ed) Proceeding of 19th International Conference on Physics of Semiconductors. Institute of physics, Warsaw, p 471 Sizmann R, Chu JH, Koch F, Ziegler J, Maier H (1990) Sub-band and resonant level spectroscopy from capacitance measurements. Semicond Sci Technol 5:S111–S114 Stern F (1972) Self-consistent results for n-type Si inversion layers. Phys Rev B 5:4891–4899 Takada Y, Uemura Y (1977) Subband structures of N-channel inversion layers on III–V compounds – possibility of the gate controlled Gunn effect. J Phys Soc Jpn 43:139–150 Takada Y, Arai K, Uchimura N, Uemura Y (1980) Theory of electronic properties in N-channel inversion layers on narrow-gap semiconductors I. Subband structure of InSb. J Phys Soc Jpn 49:1851–1858 Takada Y, Arai K, Uemura Y (1982) In: Gornik E (ed) Physics of Narrow Gap Semiconductors, Lecture Notes in Physics, Vol. 152. Springer, Berlin, p 101 Tsau GH, Sher A, Madou M, Wilson JA, Cotton VA, Jones CE (1986) Low-frequency admittance measurements on the HgCdTe/Photox SiO2 interface. J Appl Phys 59:1238–1244 van Schilfgaarde M, Kotami T, Faleev SV (2006) Adequacy of approximations in GW theory. Phys Rev B 74:245125 White AM (1981) The influence of surface properties on minority carrier lifetime and sheet conductance in semiconductors. J Phys D: Appl Phys 14:L1–L3 Xiong XM (1987) PhD thesis, Shanghai Institute of Technical Physics Yadava RDS, Sundersheshu BS, Anandan M, Bagai RK, Borle WN (1994) Precipitation in CdTe crystals studied through mie scattering. J Electron Mater 23:1349–1357 Zawadzki W (1983) Theory of optical transitions in inversion layers of narrow-gap semiconductors. J Phys C: Solid State Phys 16:229–240 Ziegler A, R¨ossler U (1988) Zener-tunnelling of inversion layer electrons on small gap semiconductors. Solid State Commun 65:805–808

Chapter 5

Superlattice and Quantum Well

5.1 Semiconductor Low-Dimensional Structures 5.1.1 Band Dispersion Relation In three-dimensional crystals, the band edge carrier motion can be described by a quasi-particle model. The interaction of the particle with the periodic crystal field is included in the effective mass, m . To first order, the electrons in the conduction band of a crystal with inversion symmetry have m independent of crystal direction, and the quasi-particle energy, E 3D , is in an isotropic distribution in k-space, E 3D .k/ D

„2 .k 2 C ky2 C kz2 /; 2m x

(5.1)

where kx , ky , kz denote the wave numbers in the x, y, z directions. If a carrier is confined in low-dimensional structures, such as a quantum well, quantum wire or dot, whose size is comparable with the De Broglie wave length of an electron, the properties of such electrons, such as their density of states (DOS), will display quantum mechanical effects. In comparison to three-dimensional bulk materials, quantum well structures have quantum confinement effects in the growth direction. In a parabolic approximation, the energy in a quantum well changes from (5.1) to: (5.2) E 2D D Ez;nz C „2 =2mxy .kx2 C ky2 /: Ez;nz can be solved from the Schr¨odinger equation in the framework of an effective mass approximation (EMA) (Weisbuch and Vinter 1991):  

 „2 @2 C V .z/ .z/ D Ez;nz .z/: 2m .z/ @z2

(5.3)

Here, m .z/ is the carrier effective mass in the well or barrier layer, V .z/ the potential profile, and Z.z/ is the envelope wave function of the confined quantum state.

J. Chu and A. Sher, Device Physics of Narrow Gap Semiconductors, Microdevices, c Springer Science+Business Media, LLC 2010 DOI 10.1007/978-1-4419-1040-0 5, 

283

284

5 Superlattice and Quantum Well

For an extreme case, i.e. an infinitely deep quantum well, V .z/ ! 1 at the well boundaries, Ez;nz in (5.2) and (5.3) has an analytical solution: Ez;nz

„2  2 D 2mz



n2z L2

 :

(5.4)

Consequently, the eigen energy of a carrier in the quantum well is comprised of a continuous part and a discrete part. Going from three to two dimensions, the band structure evolves from a continuous distribution to a series of discrete subbands. In reality, the barrier height of the quantum well is finite. For the case of a finite but deep quantum well, if the potential has even symmetry, i.e., V .z/ D V .z/ (see Fig. 5.1), the solutions of (5.3) are odd or even states. The even parity solutions are (Haug and Koch 1993; Bastard et al. 1991): ( cos kz; jzj < L=2 : (5.5) .z/ D .jzjL=2/ Be ; jzj > L=2 The odd wave functions are: ( .z/ D

sin kz;

jzj < L=2

B e .jzjL=2/ ;

jzj > L=2

:

(5.6)

In the above equations, L is the well width. The eigenvalues are determined by: 2 2 Ez;nz D „2 kz;n =2mz;w or Ez;nz D V „2 kz;n =2mz;b and 0 < Ez;nz < Vz;0 . Because z z most often the properties (e.g., effective mass, dielectric constant, and bond length) of the well material and the barrier materials are different, the boundary conditions are set by matching envelope functions at the boundary producing what are called the BenDaniel–Duke boundary conditions (BenDaniel and Duke 1966). Rather than requiring that the wave functions and their derivatives match at the boundary the both be continuous. At z D ˙L=2, the even new conditions require  and m1 d dz parity solutions of (5.5) thus satisfying the boundary conditions: .kz;nz =mz;w / tan.kz;nz L=2/ D z;nz =mz;b ;

Fig. 5.1 The energy levels and wave functions of the first and second subbands in a finite-barrier quantum well. The inflection points of the wave functions originate from differences of the effective masses in the quantum well

(5.7)

5.1 Semiconductor Low-Dimensional Structures

285

Similarly, for odd parity solutions of (5.7), to satisfy the boundary conditions requires: (5.8) .kz;nz =mz;w / tan.kz;nz L=2/ D z;nz =mz;b : Summarizing the above equations, kz;nz can be obtained from: ( z;nz D

.mz;b =mz;w /kz;nz tan.kz;nz L=2/; .mz;b =mz;w /kz;nz

tan.kz;nz L=2/ > 0

cot.kz;nz L=2/; tan.kz;nz L=2/ < 0

(5.9)

or

kz;nz D

8 ˆ ˆ ˆ ˆ ˆ
!1=2

mz;w mz;w C mz;b tan2 .kz;nz L=2/ mz;w

;

mz;w C mz;b cot2 .kz;nz L=2/

kz;0 in (5.10) is:

 kz;0 D

2mz;w Vz;0 „2

tan.kz;nz L=2/ > 0;

!1=2

(5.10) ;

tan.kz;nz L=2/ < 0;

1=2 :

(5.11)

To fully describe the subbands in stained heterojunctions, the influence of strain on the properties of the well material must be included. Strain can change the band structure, and also cause energy level splittings by reducing the band structure symmetry. The adjustment of strain at the band edge can be described by “Model-Solid” theory. It was originally proposed by Van de Walle and Martin (Van de Walle and Martin 1986, 1987; Van de Walle 1989), lately developed by many others (Satpathy et al. 1988; Wang and Stringfellow 1990; Krijin 1991; Shao et al. 2002), and used to calculate strain-induced band edge shifts. If the strained layer is a pseudo-morphic growth on a (001) substrate (Fig. 5.2), the strain can be modeled by a biaxial strain

Fig. 5.2 The schematic diagrams of the strained layers grown on a (001) substrate (a) compressive stress, (b) lattice-matched, (c) tensile stress

286

5 Superlattice and Quantum Well

coefficient parallel to the growth interface, " , and a nonaxial strain coefficient, "? , perpendicular to the growth interface, which satisfy:   a0 2C12 "k :  1 and "? D  (5.12) "k D af C11 Here, a0 is the substrate lattice constant, af is its equilibrium (without strain) lattice constant. For a zinc-blende semiconductor, the strain at the point is equivalent to the sum of a hydrostatic pressure and a uniaxial stress along the z (shear) direction. The hydrostatic pressure causes a shift of the conduction band edge Ec . The average valence band energy is Ev;av D .Ehh C Elh C Eso /=3:



 hy D av 2"k C "? Echy D ac 2"k C "? and Ev;av

(5.13)

where av and ac are hydrostatic deformation potentials of the valence and the conduction bands, respectively. Although the uniaxial shear stress doesn’t affect the conduction band’s shape at the point, it can interact with the spin–orbit effect and cause an additional splitting in the valence band. The jJ; mJ >D j3=2; 3=2 > state .Ehh /, the jJ; mJ >D j3=2; 1=2 > state .Elh /, and the jJ; mJ >D j1=2; 1=2 > state (Eso ), can all be expressed relative to the average valence band energy Eav , sh so C 001 ; 3 3  1=2 1 so sh 2 so sh 001 so 2 sh 2  C . /   001 C .001 / D ; 6 6 2 3  1=2 1 so sh 2 sh 2  001  .so /2  so sh D C . / ; (5.14) 001 001 6 6 2 3

sh D Ehh

Elhsh sh Eso

where so is the spin–orbit splitting energy without strain. In the (001) direction, sh 001 , is: C11 C 2C12 sh "; (5.15) 001 D 3b C11 b is the shear deformation potential. sh sh so sh For a zero strain, sh 001 D 0, thus Ehh D Elh D  =3, and Eso D so 2 =3. The degeneracy of Ehh and Elh is lifted in the case of a lattice matched interface, now the valence band edge is above Ev;av , i.e., so =3. In the Kelvin’s thermometric scale, the conduction and valence bands energy levels are expressed by following formulas: so C Eg;0 C Echy ; 3 hy sh D Ev;av C Ev;av C Ehh ;

Ec D Ev;av C Ehh

hy C Elhsh : Elh D Ev;av C Ev;av

(5.16)

5.1 Semiconductor Low-Dimensional Structures

287

Ev;av ; so , and Eg;0 are material parameters in the absence of strain. The band edge discontinuity between the strained well layer and the lattice matched strain free barrier layer is: Ve;0 D Ec .barrier layer/  Ec ; Vhh;0 D Ehh  Ev .barrier layer/; Vlh;0 D Elh  Ev .barrier layer/;

(5.17)

so;b ; 3 b : Ec .barrier layer/ D Ev .barrier layer/ C Eg;0

(5.18)

and b Ev .barrier layer/ D Ev;av C

In fact the parabolic band dispersion relation is only valid close to the Brillouin center, kxy D 0. As kxy increases the effective mass becomes larger. To account for this, Kane proposed a model that treats the interaction between different bands; it is especially useful for narrow gap semiconductors (Kane 1957). In a second-order approximation, the dispersion of the conduction band is: 2D .kxy / D Ez;n C Ez;n

mxy .E/ D

2 „2 kxy

2mxy .E/

;

mxy ; p 1 C 4˛.E  Ez;n /=Eg

˛D

.1  mxy =m0 /2 .3Eg2 C 4Eg so C 2.so /2 / .Eg C so /.3Eg C 2so /

:

(5.19)

Similar expressions are also valid for the light-hole valence band. For the heavyhole band, because of the high DOS at finite energy, the nonparabolic band effect is always neglected. The dispersion relation of quantum wires and dots can be obtained in a similar way. There will be new quantum effects if the carrier motion is confined in space. For a quantum wire, if the barrier is infinitely high in the z, and x directions, the energy eigenvalues become:  2  „2 ky2 n2z nx „2  2 1D Enx ;nz D C C : (5.20) 2 mx L2x mz L2z 2my The carrier energy eigenvalues also consists of a continuous and a discrete part, the difference is that two-dimensional confinement leads to a subband dispersion in a single direction. A quantum dot is a zero-dimensional system. If the barrier is assumed to be infinitely high, the 0 energy eigenvalues are: En0D x ;ny ;nz

„2  2 D 2

n2y n2z n2x C C mx L2x my L2y mz L2z

! ;

(5.21)

288

5 Superlattice and Quantum Well

nx , ny , nz are quantum numbers, they are integers but are not simultaneously equal to zero. Lx , Ly , Lz are sizes of the dot in the x, y, z directions. mx , my , mz are effective masses in the three different direction. A carrier is totally localized in a quantum dot, hence the energy levels are discrete. In reality the quantum dots are not rectangles, and the barrier height is finite. In this case, the energy eigenvalues are obtained by numerically solving t